Bis(3-chloro­benzoato-κ2O,O′)bis­(nicotinamide-κN)copper(II)

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

doi:10.1107/S1600536813014694

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Pages m356-m357

https://doi.org/10.1107/S1600536813014694

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Bis(3-chlorobenzoato-κ²O,O′)bis(nicotinamide-κN)copper(II)

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

^aKafkas University, Department of Chemistry, 63100 Kars, Turkey, ^bAksaray University, Department of Physics, 68100, Aksaray, Turkey, ^cDepartment of Physics, Sakarya University, 54187 Esentepe, Sakarya, Turkey, and ^dHacettepe University, Department of Physics, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 9 May 2013; accepted 28 May 2013; online 8 June 2013)

The molecule of the title Cu^II complex, [Cu(C₇H₄ClO₂)₂(C₆H₆N₂O)₂], contains two 3-chlorobenzoate (CB) and two nicotinamide (NA) ligands; the CB act as bidentate ligands, while the NA are monodentate ligands. The resulting CuN₂O₄ coordination polyhedron is a considerably distorted octahedron. The dihedral angles between the carboxylate groups and the adjacent benzene rings are 17.92 (12) and 24.69 (16)°, while the two benzene rings and the two pyridine rings are oriented at dihedral angles of 52.20 (8) and 1.56 (6)°. In the crystal, N—H⋯N and C—H⋯O hydrogen bonds link the molecules into a three–dimensional network. The π–π contact between the benzene rings [centroid–centroid distance = 3.982 (2) Å] may further stabilize the crystal structure.

Related literature

For niacin, see: Krishnamachari (1974 ). For the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Greenaway et al. (1984 ); Hökelek & Necefoğlu (1996 ); Hökelek et al. (1996 ); Hökelek, Dal et al. (2009 ); Hökelek, Yılmaz et al. (2009 ); Necefoğlu et al. (2011 ); Sertçelik et al. (2013 ).

Experimental

Crystal data

[Cu(C₇H₄ClO₂)₂(C₆H₆N₂O)₂]
M_r = 618.91
Triclinic, $[P \overline 1]$
a = 9.6614 (2) Å
b = 12.5429 (3) Å
c = 12.8728 (3) Å
α = 61.598 (2)°
β = 87.386 (3)°
γ = 77.115 (3)°
V = 1334.30 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 296 K
0.35 × 0.20 × 0.15 mm

Data collection

Bruker SMART BREEZE CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ) T_min = 0.774, T_max = 0.852
19053 measured reflections
5434 independent reflections
4970 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.083
S = 1.06
5434 reflections
368 parameters
117 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.80 (2)	2.12 (2)	2.896 (2)	164 (2)
N2—H2B⋯O6ⁱⁱ	0.84 (3)	2.02 (3)	2.790 (2)	153 (2)
N4—H4A⋯O5ⁱ	0.83 (3)	2.01 (3)	2.817 (2)	164 (2)
N4—H4B⋯O4ⁱⁱ	0.81 (2)	2.05 (2)	2.836 (2)	162 (3)
C19—H19⋯O1ⁱⁱⁱ	0.93	2.45	3.100 (2)	127
C21—H21⋯O5ⁱ	0.93	2.56	3.416 (2)	154
C24—H24⋯O3^iv	0.93	2.59	3.475 (3)	158
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x, -y+2, -z+1; (iii) -x+1, -y+2, -z; (iv) -x, -y+2, -z.

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: https://doi.org/10.1107/S1600536813014694/rk2404sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813014694/rk2404Isup2.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, an important respiratory stimulant (Bigoli et al., 1972), the title compound was synthesized and its crystal structure is reported herein.

In the monomeric title complex, I, the Cu^II ion is surrounded by two 3–chlorobenzoate (CB) and two (NA) ligands. The CB act as bidentate ligands, while the NA are monodentate ligands. The structures of similar complexes of Zn(II) and Cd(II) ions, [Zn₂(C₁₀H₁₄N₂O)₂(C₇H₅O₃)₄]^.2H₂O, II, (Hökelek & Necefoğlu, 1996), [Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)^.2H₂O], III, (Hökelek, Dal et al., 2009) and [Cd(C₈H₅O₃)₂(C₆H₆N₂O)₂]^.H₂O, IV, (Hökelek, Yılmaz et al., 2009) have also been determined.

In the title compound (Fig. 1), the Cu atom is displaced out of the least–squares planes of the carboxylate groups (O1/C1/O2) and (O3/C8/O4) by 0.1556 (2)Å and -0.0577 (2)Å, respectively. The dihedral angle between the planar carboxylate groups and the adjacent benzene rings A (C2—C7) and B (C9—C14) are 17.92 (12)° and 24.69 (16)°, respectively, while those between rings A, B, C (N1/C15—C19) and D (N3/C21—C25) are A/B = 52.20 (8)°, A/C = 85.61 (7)°, A/D = 84.86 (7)°, B/C = 71.49 (7)°, B/D = 69.95 (6)° and C/D = 1.56 (6)°. The two four–membered rings, (Cu1/O1/O2/C1) and (Cu1/O3/O4/C8), are oriented at a dihedral angle of 12.07 (7)°.

In I, the O1–Cu1–O2 and O3–Cu1–O4 angles are 59.76 (5)° and 55.08 (5)°, respectively. The corresponding O–M–O (where M is a metal) angles are 58.3 (3)° in II, 60.03 (6)° in III, 52.91 (4) and 53.96 (4)° in IV, 53.50 (14)° in [Cu₂(C₈H₅O₃)₄(C₆H₆N₂O)₄], V, (Sertçelik et al., 2013), 57.75 (2)° in [Cu(C₇H₄FO₂)₂(C₇H₅FO₂)(C₆H₆N₂O)₂], VI, (Necefoğlu et al., 2011), 58.3 (3)° in [Cu(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂], VII, (Hökelek et al., 1996) and 55.2 (1)° in [Cu(Asp)₂(Py)₂], where Asp is acetylsalicylate and Py is pyridine, VIII, (Greenaway et al., 1984).

In the crystal structure, intermolecular N—H···O and C—H···O hydrogen bonds (Table 1) link the molecules into a three–dimensional network, in which they may be effective in the stabilization of the structure. The π–π contact between the benzene rings, Cg2···Cg2ⁱ, where Cg2 is the centroid of the ring B (C9–C14) may further stabilize the structure, with Cg···Cg distance of 3.982 (2)Å. Symmetry code: (i) -x, 1-y, -z.

Related literature top

For niacin, see: Krishnamachari (1974). For the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Greenaway et al. (1984); Hökelek & Necefoğlu (1996); Hökelek et al. (1996); Hökelek, Dal et al. (2009); Hökelek, Yılmaz et al. (2009); Necefoğlu et al. (2011); Sertçelik et al. (2013).

Experimental top

The title compound was prepared by the reaction of CuSO₄^.5H₂O (1.25 g, 5 mmol) in H₂O (50 ml) and NA (1.22 g, 10 mmol) in H₂O (50 ml) with sodium 3–chlorobenzoate (1.79 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving blue single crystals.

Structure description top

For niacin, see: Krishnamachari (1974). For the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Greenaway et al. (1984); Hökelek & Necefoğlu (1996); Hökelek et al. (1996); Hökelek, Dal et al. (2009); Hökelek, Yılmaz et al. (2009); Necefoğlu et al. (2011); Sertçelik et al. (2013).

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 compound with the atom–numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.

Bis(3-chlorobenzoato-κ²O,O')bis(nicotinamide-κN)copper(II) top

Crystal data top

[Cu(C₇H₄ClO₂)₂(C₆H₆N₂O)₂]	Z = 2
M_r = 618.91	F(000) = 630
Triclinic, P1	D_x = 1.541 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6614 (2) Å	Cell parameters from 9977 reflections
b = 12.5429 (3) Å	θ = 2.2–28.3°
c = 12.8728 (3) Å	µ = 1.07 mm⁻¹
α = 61.598 (2)°	T = 296 K
β = 87.386 (3)°	Block, blue
γ = 77.115 (3)°	0.35 × 0.20 × 0.15 mm
V = 1334.30 (6) Å³

Data collection top

Bruker SMART BREEZE CCD diffractometer	5434 independent reflections
Radiation source: fine–focus sealed tube	4970 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 26.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −12→12
T_min = 0.774, T_max = 0.852	k = −15→15
19053 measured reflections	l = −16→16

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0431P)² + 0.6228P] where P = (F_o² + 2F_c²)/3
5434 reflections	(Δ/σ)_max = 0.001
368 parameters	Δρ_max = 0.43 e Å⁻³
117 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

[Cu(C₇H₄ClO₂)₂(C₆H₆N₂O)₂]	γ = 77.115 (3)°
M_r = 618.91	V = 1334.30 (6) Å³
Triclinic, P1	Z = 2
a = 9.6614 (2) Å	Mo Kα radiation
b = 12.5429 (3) Å	µ = 1.07 mm⁻¹
c = 12.8728 (3) Å	T = 296 K
α = 61.598 (2)°	0.35 × 0.20 × 0.15 mm
β = 87.386 (3)°

Data collection top

Bruker SMART BREEZE CCD diffractometer	5434 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	4970 reflections with I > 2σ(I)
T_min = 0.774, T_max = 0.852	R_int = 0.022
19053 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	117 restraints
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.43 e Å⁻³
5434 reflections	Δρ_min = −0.43 e Å⁻³
368 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.27888 (2)	1.000999 (18)	0.199774 (17)	0.02922 (8)
Cl1	0.80542 (9)	0.43210 (7)	0.58781 (9)	0.0953 (3)
Cl2	−0.34732 (8)	1.57612 (7)	−0.04862 (10)	0.1008 (3)
O1	0.38881 (17)	0.84400 (13)	0.15270 (12)	0.0491 (4)
O2	0.39807 (13)	0.83886 (11)	0.32503 (11)	0.0345 (3)
O3	0.18430 (14)	1.14369 (12)	0.05257 (11)	0.0375 (3)
O4	0.0977 (2)	1.19856 (14)	0.18577 (12)	0.0570 (4)
O5	0.76794 (14)	1.14536 (16)	0.40191 (15)	0.0545 (4)
O6	−0.25440 (15)	0.82581 (19)	0.51564 (15)	0.0641 (5)
N1	0.43976 (16)	1.08071 (13)	0.18924 (12)	0.0318 (3)
N2	0.54419 (18)	1.16359 (17)	0.45497 (15)	0.0398 (4)
H2A	0.565 (2)	1.176 (2)	0.507 (2)	0.040 (6)*
H2B	0.458 (3)	1.172 (2)	0.440 (2)	0.050 (6)*
N3	0.10420 (15)	0.93169 (13)	0.24499 (12)	0.0315 (3)
N4	−0.04948 (19)	0.83277 (19)	0.58345 (16)	0.0435 (4)
H4A	0.034 (3)	0.841 (2)	0.574 (2)	0.048 (6)*
H4B	−0.079 (3)	0.818 (2)	0.648 (2)	0.058 (7)*
C1	0.4330 (2)	0.78886 (17)	0.25815 (16)	0.0354 (4)
C2	0.5297 (2)	0.66138 (17)	0.31005 (18)	0.0411 (4)
C3	0.6115 (2)	0.61181 (18)	0.4143 (2)	0.0448 (5)
H3	0.6067	0.6566	0.4553	0.054*
C4	0.7010 (2)	0.4944 (2)	0.4575 (2)	0.0551 (6)
C5	0.7073 (3)	0.4258 (2)	0.3993 (3)	0.0701 (7)
H5	0.7664	0.3465	0.4298	0.084*
C6	0.6252 (4)	0.4758 (2)	0.2957 (3)	0.0791 (9)
H6	0.6283	0.4298	0.2560	0.095*
C7	0.5381 (3)	0.5933 (2)	0.2499 (2)	0.0640 (7)
H7	0.4848	0.6272	0.1785	0.077*
C8	0.1053 (2)	1.21991 (17)	0.08210 (16)	0.0377 (4)
C9	0.0182 (2)	1.33707 (17)	−0.01605 (17)	0.0391 (4)
C10	−0.1053 (2)	1.39805 (18)	0.0098 (2)	0.0487 (5)
H10	−0.1309	1.3691	0.0875	0.058*
C11	−0.1900 (2)	1.5022 (2)	−0.0812 (2)	0.0582 (6)
C12	−0.1515 (3)	1.5492 (2)	−0.1967 (2)	0.0668 (7)
H12	−0.2098	1.6192	−0.2573	0.080*
C13	−0.0263 (3)	1.4911 (2)	−0.2205 (2)	0.0640 (6)
H13	0.0021	1.5236	−0.2975	0.077*
C14	0.0587 (3)	1.3845 (2)	−0.13122 (18)	0.0498 (5)
H14	0.1426	1.3448	−0.1486	0.060*
C15	0.47759 (18)	1.09464 (16)	0.28005 (14)	0.0307 (3)
H15	0.4211	1.0749	0.3442	0.037*
C16	0.59731 (17)	1.13714 (15)	0.28251 (15)	0.0297 (3)
C17	0.6804 (2)	1.16596 (19)	0.18655 (18)	0.0412 (4)
H17	0.7637	1.1914	0.1866	0.049*
C18	0.6388 (2)	1.1566 (2)	0.09122 (18)	0.0474 (5)
H18	0.6915	1.1789	0.0248	0.057*
C19	0.5179 (2)	1.11393 (19)	0.09505 (16)	0.0405 (4)
H19	0.4899	1.1080	0.0302	0.049*
C20	0.64242 (18)	1.14888 (16)	0.38547 (16)	0.0334 (4)
C21	0.05121 (18)	0.90891 (16)	0.34942 (15)	0.0308 (3)
H21	0.0993	0.9225	0.4014	0.037*
C22	−0.07235 (18)	0.86597 (16)	0.38352 (15)	0.0319 (4)
C23	−0.1438 (2)	0.8479 (2)	0.30439 (18)	0.0444 (5)
H23	−0.2282	0.8210	0.3234	0.053*
C24	−0.0884 (2)	0.8701 (2)	0.19695 (19)	0.0494 (5)
H24	−0.1344	0.8574	0.1432	0.059*
C25	0.0353 (2)	0.91112 (19)	0.17077 (17)	0.0408 (4)
H25	0.0728	0.9252	0.0987	0.049*
C26	−0.13259 (19)	0.84043 (18)	0.50037 (17)	0.0380 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03384 (13)	0.03311 (12)	0.02251 (11)	−0.01037 (9)	0.00167 (8)	−0.01354 (9)
Cl1	0.0746 (5)	0.0701 (4)	0.1137 (7)	0.0100 (4)	−0.0438 (5)	−0.0290 (4)
Cl2	0.0536 (4)	0.0683 (4)	0.1427 (8)	0.0039 (3)	0.0142 (4)	−0.0287 (5)
O1	0.0689 (10)	0.0471 (8)	0.0279 (7)	−0.0023 (7)	0.0038 (6)	−0.0200 (6)
O2	0.0412 (7)	0.0358 (6)	0.0285 (6)	−0.0055 (5)	0.0001 (5)	−0.0180 (5)
O3	0.0451 (7)	0.0373 (6)	0.0279 (6)	−0.0085 (6)	−0.0017 (5)	−0.0138 (5)
O4	0.0919 (12)	0.0461 (8)	0.0290 (7)	−0.0090 (8)	0.0040 (7)	−0.0175 (6)
O5	0.0295 (7)	0.0882 (11)	0.0697 (10)	−0.0180 (7)	0.0031 (7)	−0.0548 (9)
O6	0.0336 (8)	0.1099 (14)	0.0543 (10)	−0.0324 (8)	0.0127 (7)	−0.0376 (10)
N1	0.0362 (7)	0.0352 (7)	0.0256 (7)	−0.0118 (6)	0.0024 (6)	−0.0144 (6)
N2	0.0334 (9)	0.0622 (11)	0.0368 (9)	−0.0152 (7)	0.0031 (7)	−0.0322 (8)
N3	0.0344 (7)	0.0346 (7)	0.0266 (7)	−0.0093 (6)	0.0006 (6)	−0.0148 (6)
N4	0.0315 (9)	0.0711 (12)	0.0331 (9)	−0.0195 (8)	0.0094 (7)	−0.0262 (8)
C1	0.0398 (9)	0.0360 (9)	0.0327 (9)	−0.0111 (7)	0.0080 (7)	−0.0177 (7)
C2	0.0451 (11)	0.0366 (9)	0.0419 (10)	−0.0110 (8)	0.0123 (8)	−0.0192 (8)
C3	0.0408 (10)	0.0402 (10)	0.0536 (12)	−0.0091 (8)	0.0040 (9)	−0.0226 (9)
C4	0.0400 (11)	0.0442 (11)	0.0685 (15)	−0.0062 (9)	0.0014 (10)	−0.0181 (11)
C5	0.0697 (16)	0.0405 (12)	0.088 (2)	0.0011 (11)	0.0127 (14)	−0.0276 (13)
C6	0.114 (2)	0.0505 (14)	0.0786 (19)	−0.0030 (15)	0.0115 (17)	−0.0426 (14)
C7	0.0931 (19)	0.0480 (12)	0.0525 (14)	−0.0053 (12)	0.0044 (13)	−0.0300 (11)
C8	0.0476 (10)	0.0350 (9)	0.0313 (9)	−0.0130 (8)	0.0014 (8)	−0.0148 (7)
C9	0.0482 (11)	0.0327 (9)	0.0353 (10)	−0.0133 (8)	0.0000 (8)	−0.0134 (8)
C10	0.0497 (12)	0.0373 (10)	0.0529 (12)	−0.0149 (9)	0.0078 (9)	−0.0148 (9)
C11	0.0430 (12)	0.0389 (11)	0.0801 (17)	−0.0089 (9)	−0.0009 (11)	−0.0183 (11)
C12	0.0701 (16)	0.0426 (12)	0.0636 (16)	−0.0101 (11)	−0.0198 (13)	−0.0054 (11)
C13	0.0832 (18)	0.0534 (13)	0.0370 (12)	−0.0156 (12)	−0.0041 (11)	−0.0065 (10)
C14	0.0611 (13)	0.0457 (11)	0.0361 (10)	−0.0123 (10)	0.0024 (9)	−0.0144 (9)
C15	0.0330 (8)	0.0365 (8)	0.0243 (8)	−0.0123 (7)	0.0053 (6)	−0.0143 (7)
C16	0.0282 (8)	0.0321 (8)	0.0296 (8)	−0.0081 (6)	0.0031 (6)	−0.0150 (7)
C17	0.0364 (10)	0.0513 (11)	0.0419 (10)	−0.0188 (8)	0.0117 (8)	−0.0239 (9)
C18	0.0488 (11)	0.0652 (13)	0.0333 (10)	−0.0234 (10)	0.0183 (8)	−0.0245 (10)
C19	0.0464 (11)	0.0525 (11)	0.0277 (9)	−0.0152 (9)	0.0073 (8)	−0.0219 (8)
C20	0.0296 (8)	0.0374 (9)	0.0374 (9)	−0.0096 (7)	0.0001 (7)	−0.0203 (8)
C21	0.0312 (8)	0.0375 (9)	0.0276 (8)	−0.0104 (7)	0.0000 (6)	−0.0174 (7)
C22	0.0286 (8)	0.0351 (8)	0.0315 (9)	−0.0074 (7)	−0.0009 (7)	−0.0151 (7)
C23	0.0392 (10)	0.0553 (12)	0.0450 (11)	−0.0207 (9)	−0.0010 (8)	−0.0244 (10)
C24	0.0547 (12)	0.0657 (13)	0.0436 (11)	−0.0237 (11)	−0.0028 (9)	−0.0339 (10)
C25	0.0492 (11)	0.0500 (11)	0.0302 (9)	−0.0150 (9)	0.0018 (8)	−0.0231 (8)
C26	0.0279 (9)	0.0484 (10)	0.0370 (10)	−0.0114 (8)	0.0050 (7)	−0.0188 (8)

Geometric parameters (Å, º) top

Cu1—O1	2.3487 (14)	C6—H6	0.9300
Cu1—O2	2.0168 (12)	C7—C6	1.376 (4)
Cu1—O3	1.9574 (12)	C7—H7	0.9300
Cu1—O4	2.6280 (12)	C8—C9	1.498 (3)
Cu1—N1	1.9947 (14)	C9—C10	1.385 (3)
Cu1—N3	2.0065 (14)	C9—C14	1.384 (3)
Cu1—C1	2.5090 (18)	C10—C11	1.379 (3)
Cl1—C4	1.731 (3)	C10—H10	0.9300
Cl2—C11	1.740 (3)	C11—C12	1.382 (4)
O1—C1	1.237 (2)	C12—H12	0.9300
O2—C1	1.281 (2)	C13—C12	1.369 (4)
O3—C8	1.279 (2)	C13—H13	0.9300
O4—C8	1.232 (2)	C14—C13	1.385 (3)
O5—C20	1.228 (2)	C14—H14	0.9300
O6—C26	1.224 (2)	C15—H15	0.9300
N1—C15	1.339 (2)	C16—C15	1.385 (2)
N1—C19	1.338 (2)	C16—C17	1.384 (2)
N2—C20	1.318 (2)	C16—C20	1.495 (2)
N2—H2A	0.79 (2)	C17—C18	1.373 (3)
N2—H2B	0.84 (3)	C17—H17	0.9300
N3—C21	1.337 (2)	C18—H18	0.9300
N3—C25	1.338 (2)	C19—C18	1.379 (3)
N4—C26	1.321 (2)	C19—H19	0.9300
N4—H4A	0.83 (3)	C21—C22	1.386 (2)
N4—H4B	0.81 (3)	C21—H21	0.9300
C1—C2	1.500 (3)	C22—C23	1.385 (3)
C2—C3	1.377 (3)	C22—C26	1.500 (3)
C2—C7	1.388 (3)	C23—C24	1.382 (3)
C3—C4	1.387 (3)	C23—H23	0.9300
C3—H3	0.9300	C24—H24	0.9300
C4—C5	1.376 (4)	C25—C24	1.371 (3)
C5—C6	1.371 (4)	C25—H25	0.9300
C5—H5	0.9300

O1—Cu1—C1	29.28 (5)	O4—C8—O3	122.57 (17)
O2—Cu1—O1	59.76 (5)	O4—C8—C9	120.80 (18)
O2—Cu1—C1	30.48 (5)	C10—C9—C8	118.89 (18)
O3—Cu1—O1	106.81 (5)	C14—C9—C8	121.26 (19)
O3—Cu1—O2	166.26 (5)	C14—C9—C10	119.85 (19)
O3—Cu1—O4	55.08 (5)	C9—C10—H10	120.4
O3—Cu1—N1	91.50 (6)	C11—C10—C9	119.2 (2)
O3—Cu1—N3	93.10 (6)	C11—C10—H10	120.4
O3—Cu1—C1	136.00 (6)	C10—C11—Cl2	119.0 (2)
N1—Cu1—O1	100.98 (6)	C10—C11—C12	121.3 (2)
N1—Cu1—O2	88.65 (5)	C12—C11—Cl2	119.71 (19)
N1—Cu1—N3	164.90 (6)	C11—C12—H12	120.5
N1—Cu1—C1	95.33 (6)	C13—C12—C11	119.0 (2)
N3—Cu1—O1	91.43 (6)	C13—C12—H12	120.5
N3—Cu1—O2	90.26 (5)	C12—C13—C14	120.7 (2)
N3—Cu1—C1	91.32 (6)	C12—C13—H13	119.6
C1—O1—Cu1	82.56 (11)	C14—C13—H13	119.6
C1—O2—Cu1	96.52 (11)	C9—C14—C13	119.8 (2)
C8—O3—Cu1	106.27 (11)	C9—C14—H14	120.1
C15—N1—Cu1	120.40 (11)	C13—C14—H14	120.1
C19—N1—Cu1	120.98 (12)	N1—C15—C16	122.74 (16)
C19—N1—C15	118.47 (15)	N1—C15—H15	118.6
C20—N2—H2A	119.4 (16)	C16—C15—H15	118.6
C20—N2—H2B	121.7 (17)	C15—C16—C20	122.86 (15)
H2A—N2—H2B	118 (2)	C17—C16—C15	117.97 (16)
C21—N3—Cu1	120.20 (11)	C17—C16—C20	119.14 (16)
C21—N3—C25	118.42 (15)	C16—C17—H17	120.3
C25—N3—Cu1	121.34 (13)	C18—C17—C16	119.43 (17)
C26—N4—H4A	122.8 (16)	C18—C17—H17	120.3
C26—N4—H4B	119.5 (18)	C17—C18—C19	119.23 (17)
H4A—N4—H4B	118 (2)	C17—C18—H18	120.4
O1—C1—Cu1	68.16 (10)	C19—C18—H18	120.4
O1—C1—O2	121.15 (17)	N1—C19—C18	122.04 (17)
O1—C1—C2	120.21 (17)	N1—C19—H19	119.0
O2—C1—Cu1	53.00 (9)	C18—C19—H19	119.0
O2—C1—C2	118.64 (16)	O5—C20—N2	122.54 (17)
C2—C1—Cu1	171.55 (14)	O5—C20—C16	119.44 (16)
C3—C2—C1	121.54 (18)	N2—C20—C16	118.02 (15)
C3—C2—C7	119.6 (2)	N3—C21—C22	122.83 (15)
C7—C2—C1	118.8 (2)	N3—C21—H21	118.6
C2—C3—C4	119.3 (2)	C22—C21—H21	118.6
C2—C3—H3	120.4	C21—C22—C26	123.15 (15)
C4—C3—H3	120.4	C23—C22—C21	117.85 (17)
C3—C4—Cl1	119.5 (2)	C23—C22—C26	118.99 (16)
C5—C4—Cl1	119.32 (19)	C22—C23—H23	120.3
C5—C4—C3	121.1 (2)	C24—C23—C22	119.42 (18)
C4—C5—H5	120.4	C24—C23—H23	120.3
C6—C5—C4	119.1 (2)	C23—C24—H24	120.5
C6—C5—H5	120.4	C25—C24—C23	118.95 (17)
C5—C6—C7	120.6 (3)	C25—C24—H24	120.5
C5—C6—H6	119.7	N3—C25—C24	122.50 (18)
C7—C6—H6	119.7	N3—C25—H25	118.8
C2—C7—H7	119.9	C24—C25—H25	118.8
C6—C7—C2	120.2 (3)	O6—C26—N4	122.87 (19)
C6—C7—H7	119.9	O6—C26—C22	119.36 (17)
O3—C8—C9	116.61 (16)	N4—C26—C22	117.76 (16)

O2—Cu1—O1—C1	−0.68 (11)	Cu1—N3—C21—C22	177.25 (13)
O3—Cu1—O1—C1	176.18 (11)	C25—N3—C21—C22	−0.5 (3)
N1—Cu1—O1—C1	81.22 (12)	Cu1—N3—C25—C24	−176.47 (16)
N3—Cu1—O1—C1	−90.14 (12)	C21—N3—C25—C24	1.3 (3)
O1—Cu1—O2—C1	0.66 (10)	O1—C1—C2—C3	161.79 (19)
O3—Cu1—O2—C1	−12.1 (3)	O1—C1—C2—C7	−17.1 (3)
N1—Cu1—O2—C1	−102.89 (11)	O2—C1—C2—C3	−18.0 (3)
N3—Cu1—O2—C1	92.17 (11)	O2—C1—C2—C7	163.1 (2)
O1—Cu1—O3—C8	169.20 (11)	C1—C2—C3—C4	−178.91 (18)
O2—Cu1—O3—C8	−179.33 (19)	C7—C2—C3—C4	0.0 (3)
N1—Cu1—O3—C8	−88.86 (12)	C1—C2—C7—C6	−179.5 (2)
N3—Cu1—O3—C8	76.76 (12)	C3—C2—C7—C6	1.5 (4)
C1—Cu1—O3—C8	171.88 (11)	C2—C3—C4—Cl1	179.33 (16)
O1—Cu1—N1—C15	−126.37 (13)	C2—C3—C4—C5	−1.3 (3)
O1—Cu1—N1—C19	49.23 (15)	Cl1—C4—C5—C6	−179.5 (2)
O2—Cu1—N1—C15	−67.55 (14)	C3—C4—C5—C6	1.1 (4)
O2—Cu1—N1—C19	108.05 (15)	C4—C5—C6—C7	0.4 (5)
O3—Cu1—N1—C15	126.19 (14)	C2—C7—C6—C5	−1.7 (5)
O3—Cu1—N1—C19	−58.21 (15)	O3—C8—C9—C10	155.12 (18)
N3—Cu1—N1—C15	18.4 (3)	O3—C8—C9—C14	−24.5 (3)
N3—Cu1—N1—C19	−165.97 (19)	O4—C8—C9—C10	−23.5 (3)
C1—Cu1—N1—C15	−97.33 (14)	O4—C8—C9—C14	156.8 (2)
C1—Cu1—N1—C19	78.27 (15)	C8—C9—C10—C11	−176.52 (18)
O1—Cu1—N3—C21	128.70 (13)	C14—C9—C10—C11	3.1 (3)
O1—Cu1—N3—C25	−53.57 (15)	C8—C9—C14—C13	178.2 (2)
O2—Cu1—N3—C21	68.94 (13)	C10—C9—C14—C13	−1.4 (3)
O2—Cu1—N3—C25	−113.33 (15)	C9—C10—C11—Cl2	178.44 (17)
O3—Cu1—N3—C21	−124.39 (13)	C9—C10—C11—C12	−2.3 (3)
O3—Cu1—N3—C25	53.34 (15)	Cl2—C11—C12—C13	178.9 (2)
N1—Cu1—N3—C21	−16.8 (3)	C10—C11—C12—C13	−0.4 (4)
N1—Cu1—N3—C25	160.9 (2)	C14—C13—C12—C11	2.1 (4)
C1—Cu1—N3—C21	99.41 (13)	C9—C14—C13—C12	−1.2 (4)
C1—Cu1—N3—C25	−82.86 (15)	C17—C16—C15—N1	−0.1 (3)
O1—Cu1—C1—O2	−178.84 (18)	C20—C16—C15—N1	−177.97 (16)
O2—Cu1—C1—O1	178.84 (18)	C15—C16—C17—C18	2.7 (3)
O3—Cu1—C1—O1	−5.26 (15)	C20—C16—C17—C18	−179.32 (18)
O3—Cu1—C1—O2	175.90 (9)	C15—C16—C20—O5	155.40 (18)
N1—Cu1—C1—O1	−102.99 (12)	C15—C16—C20—N2	−25.1 (3)
N1—Cu1—C1—O2	78.17 (11)	C17—C16—C20—O5	−22.5 (3)
N3—Cu1—C1—O1	90.58 (12)	C17—C16—C20—N2	157.06 (18)
N3—Cu1—C1—O2	−88.26 (11)	C16—C17—C18—C19	−2.6 (3)
Cu1—O1—C1—O2	1.09 (17)	N1—C19—C18—C17	−0.2 (3)
Cu1—O1—C1—C2	−178.70 (16)	N3—C21—C22—C23	−0.8 (3)
Cu1—O2—C1—O1	−1.3 (2)	N3—C21—C22—C26	−179.89 (16)
Cu1—O2—C1—C2	178.53 (14)	C21—C22—C23—C24	1.5 (3)
Cu1—O3—C8—O4	−0.1 (2)	C26—C22—C23—C24	−179.42 (19)
Cu1—O3—C8—C9	−178.74 (13)	C21—C22—C26—O6	166.2 (2)
Cu1—N1—C15—C16	173.02 (13)	C21—C22—C26—N4	−14.9 (3)
C19—N1—C15—C16	−2.7 (3)	C23—C22—C26—O6	−12.9 (3)
Cu1—N1—C19—C18	−172.84 (16)	C23—C22—C26—N4	166.07 (19)
C15—N1—C19—C18	2.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.80 (2)	2.12 (2)	2.896 (2)	164 (2)
N2—H2B···O6ⁱⁱ	0.84 (3)	2.02 (3)	2.790 (2)	153 (2)
N4—H4A···O5ⁱ	0.83 (3)	2.01 (3)	2.817 (2)	164 (2)
N4—H4B···O4ⁱⁱ	0.81 (2)	2.05 (2)	2.836 (2)	162 (3)
C19—H19···O1ⁱⁱⁱ	0.93	2.45	3.100 (2)	127
C21—H21···O5ⁱ	0.93	2.56	3.416 (2)	154
C24—H24···O3^iv	0.93	2.59	3.475 (3)	158

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

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₄ClO₂)₂(C₆H₆N₂O)₂]
M_r	618.91
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.6614 (2), 12.5429 (3), 12.8728 (3)
α, β, γ (°)	61.598 (2), 87.386 (3), 77.115 (3)
V (Å³)	1334.30 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.07
Crystal size (mm)	0.35 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART BREEZE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012)
T_min, T_max	0.774, 0.852
No. of measured, independent and observed [I > 2σ(I)] reflections	19053, 5434, 4970
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.083, 1.06
No. of reflections	5434
No. of parameters	368
No. of restraints	117
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.43

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).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.80 (2)	2.12 (2)	2.896 (2)	164 (2)
N2—H2B···O6ⁱⁱ	0.84 (3)	2.02 (3)	2.790 (2)	153 (2)
N4—H4A···O5ⁱ	0.83 (3)	2.01 (3)	2.817 (2)	164 (2)
N4—H4B···O4ⁱⁱ	0.81 (2)	2.05 (2)	2.836 (2)	162 (3)
C19—H19···O1ⁱⁱⁱ	0.93	2.45	3.100 (2)	127
C21—H21···O5ⁱ	0.93	2.56	3.416 (2)	154
C24—H24···O3^iv	0.93	2.59	3.475 (3)	158

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

Acknowledgements

The authors are indebted to Aksaray University and the Science and Technology Application and Research Center of Aksaray University, Aksaray, Turkey, for the use of X–ray diffractometer.

References

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