Aqua­bis­(3-chloro­benzoato-κO)bis­(N,N-di­ethyl­nicotinamide-κN)copper(II)

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

doi:10.1107/S1600536813018989

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages m458-m459

doi:10.1107/S1600536813018989

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Aquabis(3-chlorobenzoato-κO)bis(N,N-diethylnicotinamide-κN)copper(II)

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

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

(Received 4 July 2013; accepted 9 July 2013; online 17 July 2013)

The title compound, [Cu(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)], has twofold symmetry with the Cu^II cation and the O atom of the coordinating water molecule located on the axis. The Cu^II cation is coordinated by two carboxylate O atoms of chlorobenzoate (CB) anions, two N atoms of N,N-diethylnicotinamide (DENA) ligands and one water molecule in a distorted N₂O₃ square-pyramidal geometry. The benzene and pyridine rings are oriented at a dihedral angle of 82.51 (6)°. In the anionic ligand, the carboxylate group is twisted away from the attached benzene ring by 12.85 (11)°. In the crystal, O—H⋯O hydrogen bonds between the coordinating water molecule and the carboxyl group link the complex molecules into supramolecular chains running along the c-axis direction.

Related literature

For literature on niacin, see: Krishnamachari (1974 ). For information on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Hökelek et al. (1996 , 2009a ,b ); Hökelek & Necefoğlu (1998 , 2007 ); Necefoğlu et al. (2011a ,b ,c ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Cu(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)]
M_r = 749.13
Orthorhombic, I b a 2
a = 15.9185 (9) Å
b = 19.2366 (11) Å
c = 11.5535 (7) Å
V = 3537.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.82 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 = 0.821, T_max = 0.884
75834 measured reflections
6232 independent reflections
5189 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.086
S = 1.06
6232 reflections
224 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.39 e Å⁻³
Absolute structure: Flack (1983 ), with no Friedel pairs measured
Flack parameter: 0.027 (10)

Table 1
Selected bond lengths (Å)

Cu1—N1	2.0294 (12)
Cu1—O1	1.9337 (10)
Cu1—O4	2.238 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O2ⁱ	0.79 (4)	1.95 (3)	2.7367 (17)	171 (4)
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813018989/xu5719sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813018989/xu5719Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigations of 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 asymmetric unit of the title mononuclear Cu^II complex, (Fig. 1), contains one-half molecule, the Cu^II cation is located on a twofold rotation axis and is coordinated by carboxylate O atoms of two chlorobenzoate (CB) anions, N atoms of two N,N-diethylnicotinamide (DENA) ligands and by one water molecule, located on a twofold rotation axis, all ligands coordinating in a monodentate manner. The crystal structures of similar complexes of Cu^II, Co^II, Ni^II, Mn^II and Zn^II cations, [Cu(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1996); [Cu(C₉H₉O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011a); [Cu(C₇H₄FO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011b); [Co(C₆H₆N₂O)₂(C₇H₄NO₄)₂(H₂O)₂] (Hökelek & Necefoğlu, 1998); [Co(C₉H₉O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011c); [Ni(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009a); [Mn(C₉H₁₀NO₂)₂(H₂O)₄].2H₂O (Hökelek & Necefoğlu, 2007) and [Zn(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009b) have also been reported. In the first copper(II) complex mentioned above the two benzoate ions coordinate to the Cu^II atom as bidentate ligands, while in the other structures all the ligands coordinate in a monodentate manner.

In the title complex, the four symmetry related O and N atoms (O1, O1a and N1, N1a) [symmetry code: (a) - x, 1 - y, z] in the equatorial plane around the Cu^II cation form a distorted square-planar arrangement, while the distorted square-pyramidal coordination is completed by the water O atom (O4) in the axial position.

The Cu—O bond lengths are 1.9346 (11) Å (for benzoate oxygen) and 2.238 (2) Å (for water oxygen), and the Cu—N bond length is 2.0303 (14) Å, close to standard values (Allen et al., 1987). The Cu atom is displaced out of the mean-plane of the carboxylate group (O1/C1/O2) by -0.1606 (1) Å. The dihedral angle between the planar carboxylate group and the adjacent benzene ring A (C2—C7) is 12.85 (11)°. The benzene A (C2—C7) and the pyridine B (N1/C8—C12) rings are oriented at a dihedral angle of 82.51 (6)°.

In the crystal, strong O—H···O hydrogen bonds (Table 2) link the water hydrogens to the carboxylate oxygens into infinite chains along the c-axis.

Related literature top

For literature on niacin, see: Krishnamachari (1974). For information on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Hökelek et al. (1996, 2009a,b); Hökelek & Necefoğlu (1998, 2007); Necefoğlu et al. (2011a,b,c). For bond-length data, see: Allen et al. (1987).

Experimental top

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

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

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

Aquabis(3-chlorobenzoato-κO)bis(N,N-diethylnicotinamide-κN)copper(II) top

Crystal data top

[Cu(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)]	F(000) = 1556
M_r = 749.13	D_x = 1.406 Mg m⁻³
Orthorhombic, Iba2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I 2 -2c	Cell parameters from 9278 reflections
a = 15.9185 (9) Å	θ = 2.2–30.7°
b = 19.2366 (11) Å	µ = 0.82 mm⁻¹
c = 11.5535 (7) Å	T = 296 K
V = 3537.9 (4) Å³	Block, blue
Z = 4	0.35 × 0.20 × 0.15 mm

Data collection top

Bruker SMART BREEZE CCD diffractometer	6232 independent reflections
Radiation source: fine-focus sealed tube	5189 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ϕ and ω scans	θ_max = 32.3°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −23→23
T_min = 0.821, T_max = 0.884	k = −28→28
75834 measured reflections	l = −17→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.049P)² + 0.4582P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
6232 reflections	Δρ_max = 0.25 e Å⁻³
224 parameters	Δρ_min = −0.39 e Å⁻³
1 restraint	Absolute structure: Flack (1983), with no Friedel pairs measured
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.027 (10)

Crystal data top

[Cu(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)]	V = 3537.9 (4) Å³
M_r = 749.13	Z = 4
Orthorhombic, Iba2	Mo Kα radiation
a = 15.9185 (9) Å	µ = 0.82 mm⁻¹
b = 19.2366 (11) Å	T = 296 K
c = 11.5535 (7) Å	0.35 × 0.20 × 0.15 mm

Data collection top

Bruker SMART BREEZE CCD diffractometer	6232 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	5189 reflections with I > 2σ(I)
T_min = 0.821, T_max = 0.884	R_int = 0.048
75834 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.086	Δρ_max = 0.25 e Å⁻³
S = 1.06	Δρ_min = −0.39 e Å⁻³
6232 reflections	Absolute structure: Flack (1983), with no Friedel pairs measured
224 parameters	Absolute structure parameter: 0.027 (10)
1 restraint

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cu1	1.0000	0.5000	0.41873 (3)	0.03000 (6)
Cl1	1.46828 (3)	0.59979 (3)	0.63513 (5)	0.06445 (15)
O1	1.11786 (6)	0.52434 (6)	0.41852 (13)	0.0393 (2)
O2	1.14688 (8)	0.52348 (10)	0.60832 (13)	0.0614 (4)
O3	0.84439 (11)	0.72659 (11)	0.16031 (16)	0.0800 (5)
O4	1.0000	0.5000	0.22505 (18)	0.0538 (6)
H41	1.0395 (19)	0.4937 (15)	0.185 (4)	0.083 (10)*
N1	0.96843 (7)	0.60210 (6)	0.42656 (14)	0.0353 (2)
N2	0.74305 (10)	0.72799 (9)	0.29566 (14)	0.0469 (3)
C1	1.16668 (9)	0.52875 (9)	0.50510 (15)	0.0363 (3)
C2	1.25768 (9)	0.54254 (8)	0.47400 (14)	0.0349 (3)
C3	1.31396 (9)	0.56202 (9)	0.56019 (15)	0.0391 (3)
H3	1.2964	0.5673	0.6364	0.047*
C4	1.39704 (10)	0.57329 (8)	0.52927 (16)	0.0414 (3)
C5	1.42506 (9)	0.56541 (8)	0.4176 (2)	0.0469 (3)
H5	1.4812	0.5729	0.3992	0.056*
C6	1.36773 (12)	0.54600 (10)	0.33236 (19)	0.0514 (4)
H6	1.3857	0.5403	0.2563	0.062*
C7	1.28426 (11)	0.53510 (9)	0.36030 (17)	0.0422 (4)
H7	1.2460	0.5228	0.3030	0.051*
C8	0.90811 (10)	0.62540 (8)	0.35534 (15)	0.0372 (3)
H8	0.8802	0.5936	0.3084	0.045*
C9	0.88569 (10)	0.69476 (8)	0.34881 (14)	0.0398 (3)
C10	0.92796 (12)	0.74174 (8)	0.4190 (2)	0.0510 (4)
H10	0.9146	0.7888	0.4161	0.061*
C11	0.99002 (12)	0.71828 (10)	0.4931 (2)	0.0509 (4)
H11	1.0188	0.7490	0.5409	0.061*
C12	1.00827 (10)	0.64755 (10)	0.49440 (18)	0.0412 (3)
H12	1.0497	0.6314	0.5443	0.049*
C13	0.82193 (13)	0.71794 (10)	0.26044 (15)	0.0462 (4)
C14	0.71426 (12)	0.71772 (12)	0.4142 (2)	0.0551 (4)
H14A	0.6784	0.7563	0.4361	0.066*
H14B	0.7625	0.7177	0.4656	0.066*
C15	0.6667 (2)	0.65112 (17)	0.4298 (3)	0.0907 (8)
H15A	0.6454	0.6486	0.5074	0.136*
H15B	0.7036	0.6125	0.4159	0.136*
H15C	0.6208	0.6496	0.3760	0.136*
C16	0.68061 (14)	0.75374 (11)	0.2115 (2)	0.0546 (5)
H16A	0.6255	0.7363	0.2325	0.066*
H16B	0.6943	0.7358	0.1353	0.066*
C17	0.6778 (2)	0.83180 (13)	0.2067 (3)	0.0864 (9)
H17A	0.6405	0.8462	0.1461	0.130*
H17B	0.7332	0.8495	0.1916	0.130*
H17C	0.6581	0.8496	0.2795	0.130*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02380 (9)	0.03532 (10)	0.03087 (11)	0.00119 (8)	0.000	0.000
Cl1	0.0404 (2)	0.0777 (3)	0.0752 (4)	−0.0116 (2)	−0.0184 (2)	0.0065 (3)
O1	0.0265 (4)	0.0465 (5)	0.0449 (5)	−0.0019 (4)	−0.0005 (5)	−0.0018 (7)
O2	0.0334 (6)	0.1087 (12)	0.0420 (7)	−0.0084 (7)	0.0062 (5)	0.0074 (8)
O3	0.0700 (10)	0.1258 (14)	0.0442 (8)	0.0380 (10)	0.0141 (8)	0.0253 (10)
O4	0.0329 (9)	0.1020 (18)	0.0265 (10)	0.0133 (9)	0.000	0.000
N1	0.0290 (5)	0.0383 (5)	0.0385 (7)	0.0010 (4)	0.0002 (6)	−0.0028 (6)
N2	0.0421 (7)	0.0617 (8)	0.0369 (7)	0.0086 (6)	−0.0025 (6)	−0.0013 (7)
C1	0.0271 (6)	0.0404 (8)	0.0414 (8)	0.0011 (5)	0.0034 (5)	0.0022 (6)
C2	0.0259 (6)	0.0380 (7)	0.0408 (8)	0.0008 (5)	0.0023 (6)	0.0036 (6)
C3	0.0304 (6)	0.0462 (8)	0.0409 (8)	−0.0006 (6)	−0.0011 (6)	0.0060 (6)
C4	0.0292 (6)	0.0394 (7)	0.0556 (10)	−0.0005 (6)	−0.0050 (6)	0.0073 (7)
C5	0.0283 (6)	0.0440 (7)	0.0683 (10)	−0.0026 (5)	0.0105 (8)	0.0012 (10)
C6	0.0425 (9)	0.0593 (10)	0.0523 (11)	−0.0073 (7)	0.0181 (8)	−0.0060 (8)
C7	0.0353 (7)	0.0488 (9)	0.0426 (9)	−0.0033 (6)	0.0052 (7)	−0.0042 (7)
C8	0.0340 (7)	0.0392 (7)	0.0385 (8)	0.0023 (5)	−0.0017 (6)	−0.0016 (6)
C9	0.0390 (7)	0.0417 (7)	0.0389 (8)	0.0065 (6)	0.0043 (6)	0.0030 (6)
C10	0.0548 (9)	0.0352 (6)	0.0631 (10)	0.0041 (6)	0.0000 (11)	−0.0029 (10)
C11	0.0458 (9)	0.0426 (9)	0.0643 (12)	−0.0027 (7)	−0.0054 (8)	−0.0141 (8)
C12	0.0339 (7)	0.0463 (8)	0.0435 (9)	0.0026 (6)	−0.0029 (6)	−0.0071 (7)
C13	0.0503 (9)	0.0505 (9)	0.0377 (9)	0.0151 (8)	0.0031 (7)	0.0035 (7)
C14	0.0438 (8)	0.0812 (12)	0.0405 (8)	0.0058 (8)	0.0010 (9)	−0.0060 (12)
C15	0.099 (2)	0.0903 (18)	0.0825 (19)	−0.0149 (15)	0.0178 (19)	0.0077 (18)
C16	0.0501 (10)	0.0630 (11)	0.0508 (10)	0.0082 (8)	−0.0108 (8)	−0.0045 (9)
C17	0.094 (2)	0.0615 (13)	0.104 (2)	0.0226 (13)	−0.0383 (17)	−0.0114 (14)

Geometric parameters (Å, º) top

Cu1—N1	2.0294 (12)	C7—H7	0.9300
Cu1—N1ⁱ	2.0294 (12)	C8—H8	0.9300
Cu1—O1	1.9337 (10)	C9—C8	1.383 (2)
Cu1—O1ⁱ	1.9337 (10)	C9—C10	1.388 (3)
Cu1—O4	2.238 (2)	C9—C13	1.507 (2)
Cl1—C4	1.7439 (18)	C10—C11	1.383 (3)
O1—C1	1.269 (2)	C10—H10	0.9300
O4—H41	0.79 (4)	C11—H11	0.9300
N1—C8	1.341 (2)	C12—C11	1.391 (3)
N1—C12	1.335 (2)	C12—H12	0.9300
N2—C13	1.334 (2)	C13—O3	1.222 (2)
N2—C14	1.458 (3)	C14—C15	1.499 (4)
N2—C16	1.476 (3)	C14—H14A	0.9700
C1—O2	1.238 (2)	C14—H14B	0.9700
C1—C2	1.516 (2)	C15—H15A	0.9600
C2—C3	1.391 (2)	C15—H15B	0.9600
C2—C7	1.387 (2)	C15—H15C	0.9600
C3—C4	1.387 (2)	C16—C17	1.503 (3)
C3—H3	0.9300	C16—H16A	0.9700
C5—C4	1.373 (3)	C16—H16B	0.9700
C5—C6	1.394 (3)	C17—H17A	0.9600
C5—H5	0.9300	C17—H17B	0.9600
C6—H6	0.9300	C17—H17C	0.9600
C7—C6	1.383 (2)

O1—Cu1—O1ⁱ	179.86 (9)	C9—C8—H8	118.6
O1—Cu1—O4	89.93 (5)	C8—C9—C10	118.11 (16)
O1ⁱ—Cu1—O4	89.93 (5)	C8—C9—C13	119.75 (16)
O1—Cu1—N1	90.35 (5)	C10—C9—C13	121.96 (15)
O1ⁱ—Cu1—N1	89.66 (5)	C9—C10—H10	120.2
O1—Cu1—N1ⁱ	89.66 (5)	C11—C10—C9	119.69 (15)
O1ⁱ—Cu1—N1ⁱ	90.35 (5)	C11—C10—H10	120.2
N1—Cu1—O4	92.55 (5)	C10—C11—C12	118.36 (17)
N1ⁱ—Cu1—O4	92.55 (5)	C10—C11—H11	120.8
N1ⁱ—Cu1—N1	174.89 (9)	C12—C11—H11	120.8
C1—O1—Cu1	127.53 (12)	N1—C12—C11	122.34 (17)
Cu1—O4—H41	126 (3)	N1—C12—H12	118.8
C8—N1—Cu1	118.25 (11)	C11—C12—H12	118.8
C12—N1—Cu1	122.85 (12)	O3—C13—N2	122.97 (18)
C12—N1—C8	118.79 (13)	O3—C13—C9	118.98 (17)
C13—N2—C14	124.25 (16)	N2—C13—C9	118.05 (16)
C13—N2—C16	118.78 (16)	N2—C14—C15	112.8 (2)
C14—N2—C16	116.93 (15)	N2—C14—H14A	109.0
O1—C1—C2	114.20 (14)	N2—C14—H14B	109.0
O2—C1—O1	126.72 (15)	C15—C14—H14A	109.0
O2—C1—C2	119.08 (15)	C15—C14—H14B	109.0
C3—C2—C1	119.53 (15)	H14A—C14—H14B	107.8
C7—C2—C1	119.85 (14)	C14—C15—H15A	109.5
C7—C2—C3	120.62 (14)	C14—C15—H15B	109.5
C2—C3—H3	120.9	C14—C15—H15C	109.5
C4—C3—C2	118.15 (16)	H15A—C15—H15B	109.5
C4—C3—H3	120.9	H15A—C15—H15C	109.5
C3—C4—Cl1	119.02 (14)	H15B—C15—H15C	109.5
C5—C4—Cl1	118.68 (12)	N2—C16—C17	112.26 (19)
C5—C4—C3	122.30 (16)	N2—C16—H16A	109.2
C4—C5—C6	118.74 (14)	N2—C16—H16B	109.2
C4—C5—H5	120.6	C17—C16—H16A	109.2
C6—C5—H5	120.6	C17—C16—H16B	109.2
C5—C6—H6	119.8	H16A—C16—H16B	107.9
C7—C6—C5	120.31 (18)	C16—C17—H17A	109.5
C7—C6—H6	119.8	C16—C17—H17B	109.5
C2—C7—H7	120.1	C16—C17—H17C	109.5
C6—C7—C2	119.87 (17)	H17A—C17—H17B	109.5
C6—C7—H7	120.1	H17A—C17—H17C	109.5
N1—C8—C9	122.71 (15)	H17B—C17—H17C	109.5
N1—C8—H8	118.6

O4—Cu1—O1—C1	−173.97 (13)	O1—C1—C2—C7	−13.2 (2)
N1—Cu1—O1—C1	93.48 (14)	O2—C1—C2—C3	−12.1 (2)
N1ⁱ—Cu1—O1—C1	−81.41 (14)	O2—C1—C2—C7	167.34 (19)
O1—Cu1—N1—C8	133.82 (13)	C1—C2—C3—C4	179.08 (15)
O1ⁱ—Cu1—N1—C8	−46.04 (13)	C7—C2—C3—C4	−0.4 (2)
O1—Cu1—N1—C12	−42.21 (15)	C1—C2—C7—C6	−178.40 (16)
O1ⁱ—Cu1—N1—C12	137.94 (15)	C3—C2—C7—C6	1.1 (3)
O4—Cu1—N1—C8	43.87 (12)	C2—C3—C4—Cl1	178.47 (12)
O4—Cu1—N1—C12	−132.15 (14)	C2—C3—C4—C5	−0.4 (2)
Cu1—O1—C1—O2	−6.0 (3)	C6—C5—C4—Cl1	−178.34 (14)
Cu1—O1—C1—C2	174.59 (9)	C6—C5—C4—C3	0.6 (3)
Cu1—N1—C8—C9	−175.86 (13)	C4—C5—C6—C7	0.1 (3)
C12—N1—C8—C9	0.3 (3)	C2—C7—C6—C5	−0.9 (3)
Cu1—N1—C12—C11	175.38 (16)	C10—C9—C8—N1	0.2 (3)
C8—N1—C12—C11	−0.6 (3)	C13—C9—C8—N1	175.42 (16)
C14—N2—C13—O3	179.6 (2)	C8—C9—C10—C11	−0.5 (3)
C14—N2—C13—C9	−0.3 (3)	C13—C9—C10—C11	−175.56 (19)
C16—N2—C13—O3	−2.8 (3)	C8—C9—C13—O3	−79.9 (3)
C16—N2—C13—C9	177.28 (16)	C8—C9—C13—N2	100.0 (2)
C13—N2—C14—C15	−102.9 (3)	C10—C9—C13—O3	95.1 (3)
C16—N2—C14—C15	79.5 (3)	C10—C9—C13—N2	−85.0 (2)
C13—N2—C16—C17	−88.5 (3)	C9—C10—C11—C12	0.2 (3)
C14—N2—C16—C17	89.2 (3)	N1—C12—C11—C10	0.4 (3)
O1—C1—C2—C3	167.34 (15)

Symmetry code: (i) −x+2, −y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2ⁱⁱ	0.79 (4)	1.95 (3)	2.7367 (17)	171 (4)

Symmetry code: (ii) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)]
M_r	749.13
Crystal system, space group	Orthorhombic, Iba2
Temperature (K)	296
a, b, c (Å)	15.9185 (9), 19.2366 (11), 11.5535 (7)
V (Å³)	3537.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.35 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART BREEZE CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2012)
T_min, T_max	0.821, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	75834, 6232, 5189
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.752

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.086, 1.06
No. of reflections	6232
No. of parameters	224
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.39
Absolute structure	Flack (1983), with no Friedel pairs measured
Absolute structure parameter	0.027 (10)

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

Selected bond lengths (Å) top

Cu1—N1	2.0294 (12)	Cu1—O4	2.238 (2)
Cu1—O1	1.9337 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2ⁱ	0.79 (4)	1.95 (3)	2.7367 (17)	171 (4)

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

The authors acknowledge the Aksaray University, Science and Technology Application and Research Center, Aksaray, Turkey, for the use of the Bruker SMART BREEZE CCD diffractometer (purchased under grant No. 2010K120480 of the State of Planning Organization).

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