Bis(acetato-κO)[1,2-bis­(2-pyridyl­meth­oxy)benzene-κ4N,O,O′,N′]copper(II) tetra­hydrate

Zhang, S.; Wang, Y.-J.; Ma, D.-S.; Liu, Y.; Gao, J.-S.

doi:10.1107/S1600536810021495

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page m787

doi:10.1107/S1600536810021495

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Bis(acetato-κO)[1,2-bis(2-pyridylmethoxy)benzene-κ⁴N,O,O′,N′]copper(II) tetrahydrate

Shuang Zhang,^a Yu-Jie Wang,^a,^b Dong-Sheng Ma,^b Ying Liu ^b and Jin-Sheng Gao ^a,^b ^*

^aEngineering Research Center of Pesticides of Heilongjiang Province, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hgf1000@163.com

(Received 1 June 2010; accepted 5 June 2010; online 16 June 2010)

In the title compound, [Cu(CH₃COO)₂(C₁₈H₁₆N₂O₂)]·4H₂O, the Cu^II ion is six-coordinated in a Jahn–Teller-distorted octahedral geometry environment defined by four O atoms and two N atoms. A chain structure along [100] is built up by intermolecular O—H⋯O hydrogen bonds involving the uncoordinated water molecules.

Related literature

For the synthesis and general backround to flexible pyridyl-based ligands, see: Liu et al. (2010a ,b ). For a related structure, see: Zhang et al. (2010 )

Experimental

Crystal data

[Cu(C₂H₃O₂)₂(C₁₈H₁₆N₂O₂)]·4H₂O
M_r = 545.02
Triclinic, $[P \overline 1]$
a = 8.0192 (16) Å
b = 11.291 (2) Å
c = 14.117 (3) Å
α = 102.97 (3)°
β = 92.69 (3)°
γ = 93.70 (3)°
V = 1240.5 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 291 K
0.37 × 0.15 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.726, T_max = 0.880
12216 measured reflections
5621 independent reflections
4677 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.169
S = 1.05
5621 reflections
318 parameters
H-atom parameters constrained
Δρ_max = 1.14 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H67⋯O6ⁱ	0.85	2.40	3.072 (6)	137
O10—H66⋯O9	0.85	2.07	2.913 (6)	169
O9—H64⋯O8ⁱⁱ	0.85	2.26	2.955 (6)	139
O9—H65⋯O8	0.85	2.09	2.828 (6)	145
O8—H63⋯O7ⁱⁱⁱ	0.85	2.06	2.874 (5)	162
O8—H62⋯O7	0.85	1.94	2.784 (5)	176
O7—H61⋯O6^iv	0.85	1.91	2.755 (4)	177
O7—H60⋯O4	0.85	1.94	2.784 (5)	172
Symmetry codes: (i) x, y-1, z; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y+2, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021495/ng2782sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810021495/ng2782Isup2.hkl

checkCIF report

Comment top

N-Heterocyclic ligands coordinated with transition metal ions can form a variety of topology structures, including macrocycles, polyhedra and linear and helical polymers. Our group has report three kinds of flexible pyridyl-based ligands in previous reports (Liu et al. 20010a; Liu et al. 20010b). As a part of our continuing work for bipyridyl aromatic ligands, we report the crystal structure of the title compound here, and its analogous monohydrate compound also has been reported by our group (Zhang et al. 20010).

1,2-Bis(pyridin-2-ylmethoxy)benzene molecule act as a chelating ligand to coordinate with Cu^II ion forming a discrete strucutre. Two acetate counter ions also coordinate to the center Cu^II ion, resulting the Cu^II ion is six-coordinated in quadrangular bipyramid geometry (Figure 1, Table 1).

A one-dimensional chain structure along [100] direction is built up by intermolecular hydrogen bonds involving the uncoordinated water molecules (Figure 2, Table 2).

Related literature top

For the synthesis and general backround to flexible pyridyl-based ligands, see: Liu et al. (2010a,b). For a related structure, see: Zhang et al. (2010)

Experimental top

The 1,2-Bis(pyridin-2-ylmethoxy)benzene was synthesized by the reaction of ο-dihydroxybenzene and 2-chloromethylpyridine hydrochloride under nitrogen atmosphere and alkaline condition (Liu et al., 2010a). Title ligand (0.58 g, 2 mmol) and Cu(CH₃COO)₂.H₂O (0.40 g, 2 mmol) were dissolved in 15 ml e thanol, and then the mixture keep stirring for 30 minute. The resulting solution was filtered, and the filtrate was allowed to stand in a desiccator at room temperature for several days. Bule needle crystals were obtained.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 30% probability level for non-H atoms.
	Fig. 2. A partial packing view, showing the one-dimensional hydrogen bonding structure along [100] direction. Dashed lines indicate the hydrogen bonds, no involving H atoms have been omitted.

Bis(acetato-κO)[1,2-bis(2-pyridylmethoxy)benzene- κ⁴N,O,O',N']copper(II) tetrahydrate top

Crystal data top

[Cu(C₂H₃O₂)₂(C₁₈H₁₆N₂O₂)]·4H₂O	Z = 2
M_r = 545.02	F(000) = 568
Triclinic, P1	D_x = 1.459 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0192 (16) Å	Cell parameters from 10671 reflections
b = 11.291 (2) Å	θ = 3.0–27.5°
c = 14.117 (3) Å	µ = 0.94 mm⁻¹
α = 102.97 (3)°	T = 291 K
β = 92.69 (3)°	Block, blue
γ = 93.70 (3)°	0.37 × 0.15 × 0.14 mm
V = 1240.5 (4) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	5621 independent reflections
Radiation source: fine-focus sealed tube	4677 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scan	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→9
T_min = 0.726, T_max = 0.880	k = −14→14
12216 measured reflections	l = −18→18

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0738P)² + 2.5027P] where P = (F_o² + 2F_c²)/3
5621 reflections	(Δ/σ)_max = 0.001
318 parameters	Δρ_max = 1.14 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Cu(C₂H₃O₂)₂(C₁₈H₁₆N₂O₂)]·4H₂O	γ = 93.70 (3)°
M_r = 545.02	V = 1240.5 (4) Å³
Triclinic, P1	Z = 2
a = 8.0192 (16) Å	Mo Kα radiation
b = 11.291 (2) Å	µ = 0.94 mm⁻¹
c = 14.117 (3) Å	T = 291 K
α = 102.97 (3)°	0.37 × 0.15 × 0.14 mm
β = 92.69 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	5621 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4677 reflections with I > 2σ(I)
T_min = 0.726, T_max = 0.880	R_int = 0.043
12216 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.169	H-atom parameters constrained
S = 1.05	Δρ_max = 1.14 e Å⁻³
5621 reflections	Δρ_min = −0.44 e Å⁻³
318 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
C1	0.6440 (5)	0.9469 (4)	0.1729 (3)	0.0424 (9)
H1	0.6547	0.9754	0.2402	0.051*
C2	0.7766 (5)	0.9716 (4)	0.1190 (4)	0.0486 (10)
H2	0.8748	1.0144	0.1496	0.058*
C3	0.7601 (6)	0.9315 (4)	0.0192 (4)	0.0509 (11)
H3	0.8460	0.9481	−0.0190	0.061*
C4	0.6143 (5)	0.8665 (4)	−0.0229 (3)	0.0452 (9)
H4	0.6007	0.8382	−0.0901	0.054*
C5	0.4872 (5)	0.8432 (3)	0.0357 (3)	0.0340 (7)
C6	0.3333 (5)	0.7660 (4)	−0.0113 (3)	0.0444 (9)
H6A	0.3042	0.7845	−0.0736	0.053*
H6B	0.3543	0.6805	−0.0226	0.053*
C7	0.0550 (5)	0.7147 (3)	0.0236 (3)	0.0374 (8)
C8	0.0090 (6)	0.6517 (4)	−0.0710 (3)	0.0475 (10)
H8	0.0775	0.6576	−0.1213	0.057*
C9	−0.1418 (6)	0.5795 (4)	−0.0894 (4)	0.0554 (12)
H9	−0.1733	0.5355	−0.1524	0.066*
C10	−0.2436 (6)	0.5729 (4)	−0.0153 (4)	0.0566 (12)
H10	−0.3444	0.5251	−0.0286	0.068*
C11	−0.1981 (5)	0.6369 (4)	0.0798 (4)	0.0491 (10)
H11	−0.2684	0.6331	0.1298	0.059*
C12	−0.0462 (5)	0.7062 (4)	0.0988 (3)	0.0393 (8)
C13	−0.0439 (6)	0.7318 (5)	0.2704 (3)	0.0531 (11)
H13	−0.1295	0.6714	0.2681	0.064*
C14	0.0544 (5)	0.8017 (4)	0.3605 (3)	0.0410 (9)
C15	−0.0073 (7)	0.8020 (6)	0.4506 (4)	0.0633 (14)
H15	−0.1091	0.7596	0.4546	0.076*
C16	0.0828 (8)	0.8653 (7)	0.5345 (4)	0.0775 (18)
H16	0.0435	0.8652	0.5955	0.093*
C17	0.2324 (6)	0.9287 (6)	0.5260 (3)	0.0640 (14)
H17	0.2947	0.9740	0.5809	0.077*
C18	0.2869 (5)	0.9233 (4)	0.4345 (3)	0.0466 (10)
H18	0.3892	0.9641	0.4289	0.056*
C19	0.4783 (5)	0.6757 (4)	0.2747 (3)	0.0357 (8)
C20	0.5151 (6)	0.5454 (4)	0.2706 (4)	0.0516 (11)
H20A	0.6264	0.5435	0.2981	0.077*
H20B	0.5062	0.5003	0.2040	0.077*
H20C	0.4360	0.5096	0.3070	0.077*
C21	0.2987 (5)	1.1144 (4)	0.2719 (3)	0.0382 (8)
C22	0.2136 (7)	1.2277 (4)	0.2681 (4)	0.0553 (11)
H22A	0.1609	1.2554	0.3280	0.083*
H22B	0.1304	1.2103	0.2147	0.083*
H22C	0.2948	1.2899	0.2593	0.083*
Cu1	0.31166 (5)	0.85895 (4)	0.22267 (3)	0.02996 (15)
N1	0.5010 (4)	0.8839 (3)	0.1325 (2)	0.0337 (6)
N2	0.2005 (4)	0.8624 (3)	0.3531 (2)	0.0362 (7)
O1	0.2007 (3)	0.7897 (3)	0.0502 (2)	0.0424 (6)
O2	0.0142 (3)	0.7724 (3)	0.1897 (2)	0.0425 (6)
O3	0.3666 (3)	0.6916 (2)	0.2120 (2)	0.0389 (6)
O4	0.5540 (4)	0.7602 (3)	0.3366 (2)	0.0463 (7)
O5	0.2292 (3)	1.0156 (2)	0.2193 (2)	0.0397 (6)
O6	0.4298 (4)	1.1202 (3)	0.3240 (2)	0.0528 (8)
O7	0.5369 (4)	0.6904 (3)	0.5132 (2)	0.0563 (8)
H60	0.5492	0.7168	0.4619	0.084*
H61	0.5436	0.7494	0.5629	0.084*
O8	0.7329 (4)	0.4974 (4)	0.5198 (3)	0.0690 (10)
H62	0.6766	0.5576	0.5164	0.103*
H63	0.6688	0.4337	0.5166	0.103*
O9	0.9449 (5)	0.4636 (4)	0.3630 (3)	0.0803 (12)
H64	1.0478	0.4888	0.3703	0.120*
H65	0.9111	0.4532	0.4169	0.120*
O10	0.7313 (7)	0.2533 (5)	0.2556 (3)	0.1047 (17)
H66	0.8015	0.3131	0.2805	0.157*
H67	0.6436	0.2585	0.2873	0.157*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0347 (19)	0.047 (2)	0.043 (2)	−0.0025 (17)	0.0035 (16)	0.0075 (17)
C2	0.035 (2)	0.044 (2)	0.066 (3)	−0.0034 (18)	0.0084 (19)	0.011 (2)
C3	0.045 (2)	0.052 (3)	0.062 (3)	0.005 (2)	0.023 (2)	0.022 (2)
C4	0.049 (2)	0.049 (2)	0.041 (2)	0.0062 (19)	0.0137 (18)	0.0161 (18)
C5	0.0377 (18)	0.0326 (17)	0.0351 (18)	0.0057 (15)	0.0077 (15)	0.0129 (14)
C6	0.046 (2)	0.052 (2)	0.0335 (19)	−0.0015 (19)	0.0022 (16)	0.0075 (17)
C7	0.0344 (18)	0.0339 (18)	0.042 (2)	0.0034 (15)	−0.0082 (15)	0.0077 (15)
C8	0.047 (2)	0.046 (2)	0.045 (2)	0.0072 (19)	−0.0079 (18)	0.0032 (18)
C9	0.054 (3)	0.044 (2)	0.061 (3)	0.002 (2)	−0.023 (2)	0.002 (2)
C10	0.049 (2)	0.043 (2)	0.074 (3)	−0.011 (2)	−0.024 (2)	0.014 (2)
C11	0.041 (2)	0.048 (2)	0.059 (3)	−0.0042 (19)	−0.0073 (19)	0.019 (2)
C12	0.0365 (19)	0.0387 (19)	0.043 (2)	0.0022 (16)	−0.0097 (16)	0.0133 (16)
C13	0.042 (2)	0.072 (3)	0.045 (2)	−0.017 (2)	0.0033 (18)	0.017 (2)
C14	0.0379 (19)	0.049 (2)	0.040 (2)	0.0039 (17)	0.0098 (16)	0.0166 (17)
C15	0.052 (3)	0.089 (4)	0.053 (3)	−0.008 (3)	0.019 (2)	0.025 (3)
C16	0.071 (3)	0.126 (6)	0.038 (3)	−0.004 (4)	0.015 (2)	0.027 (3)
C17	0.056 (3)	0.106 (4)	0.029 (2)	0.006 (3)	0.0026 (19)	0.013 (2)
C18	0.039 (2)	0.067 (3)	0.035 (2)	−0.001 (2)	−0.0006 (16)	0.0138 (19)
C19	0.0317 (17)	0.0396 (19)	0.0384 (19)	−0.0005 (15)	0.0050 (15)	0.0149 (15)
C20	0.057 (3)	0.043 (2)	0.058 (3)	0.004 (2)	−0.005 (2)	0.0181 (19)
C21	0.045 (2)	0.0383 (19)	0.0320 (18)	0.0038 (17)	0.0093 (16)	0.0088 (15)
C22	0.071 (3)	0.039 (2)	0.056 (3)	0.012 (2)	0.004 (2)	0.0091 (19)
Cu1	0.0289 (2)	0.0340 (2)	0.0271 (2)	−0.00067 (17)	0.00117 (15)	0.00810 (16)
N1	0.0333 (15)	0.0363 (16)	0.0333 (15)	0.0024 (13)	0.0064 (12)	0.0110 (12)
N2	0.0317 (15)	0.0482 (18)	0.0315 (15)	0.0077 (14)	0.0041 (12)	0.0134 (13)
O1	0.0344 (13)	0.0516 (16)	0.0367 (14)	−0.0029 (12)	−0.0009 (11)	0.0033 (12)
O2	0.0395 (14)	0.0478 (16)	0.0391 (15)	−0.0092 (13)	−0.0037 (11)	0.0121 (12)
O3	0.0397 (14)	0.0387 (14)	0.0383 (14)	0.0009 (12)	−0.0009 (11)	0.0102 (11)
O4	0.0382 (14)	0.0456 (16)	0.0517 (17)	−0.0044 (13)	−0.0063 (12)	0.0082 (13)
O5	0.0429 (15)	0.0357 (14)	0.0405 (14)	0.0025 (12)	0.0037 (11)	0.0084 (11)
O6	0.0521 (18)	0.0500 (18)	0.0505 (18)	0.0040 (15)	−0.0066 (14)	0.0011 (14)
O7	0.074 (2)	0.0462 (17)	0.0457 (17)	0.0013 (16)	−0.0037 (15)	0.0061 (13)
O8	0.0480 (19)	0.069 (2)	0.088 (3)	0.0019 (17)	0.0032 (18)	0.014 (2)
O9	0.073 (3)	0.088 (3)	0.075 (3)	0.006 (2)	−0.002 (2)	0.009 (2)
O10	0.126 (4)	0.099 (4)	0.074 (3)	−0.028 (3)	0.023 (3)	−0.006 (3)

Geometric parameters (Å, º) top

C1—N1	1.341 (5)	C16—C17	1.382 (8)
C1—C2	1.386 (6)	C16—H16	0.9300
C1—H1	0.9300	C17—C18	1.373 (6)
C2—C3	1.376 (7)	C17—H17	0.9300
C2—H2	0.9300	C18—N2	1.335 (5)
C3—C4	1.374 (7)	C18—H18	0.9300
C3—H3	0.9300	C19—O4	1.242 (5)
C4—C5	1.390 (5)	C19—O3	1.279 (5)
C4—H4	0.9300	C19—C20	1.508 (6)
C5—N1	1.337 (5)	C20—H20A	0.9600
C5—C6	1.499 (6)	C20—H20B	0.9600
C6—O1	1.406 (5)	C20—H20C	0.9600
C6—H6A	0.9700	C21—O6	1.245 (5)
C6—H6B	0.9700	C21—O5	1.271 (5)
C7—C12	1.382 (6)	C21—C22	1.498 (6)
C7—O1	1.382 (5)	C22—H22A	0.9600
C7—C8	1.385 (6)	C22—H22B	0.9600
C8—C9	1.394 (6)	C22—H22C	0.9600
C8—H8	0.9300	Cu1—O5	1.937 (3)
C9—C10	1.369 (8)	Cu1—O3	1.942 (3)
C9—H9	0.9300	Cu1—N1	2.072 (3)
C10—C11	1.394 (7)	Cu1—N2	2.076 (3)
C10—H10	0.9300	Cu1—O1	2.486 (3)
C11—C12	1.385 (6)	Cu1—O2	2.501 (3)
C11—H11	0.9300	O7—H60	0.8495
C12—O2	1.381 (5)	O7—H61	0.8496
C13—O2	1.408 (5)	O8—H62	0.8487
C13—C14	1.495 (6)	O8—H63	0.8477
C13—H13	0.9300	O9—H64	0.8487
C14—N2	1.339 (5)	O9—H65	0.8493
C14—C15	1.386 (6)	O10—H66	0.8500
C15—C16	1.382 (8)	O10—H67	0.8500
C15—H15	0.9300

N1—C1—C2	123.0 (4)	N2—C18—C17	123.4 (4)
N1—C1—H1	118.5	N2—C18—H18	118.3
C2—C1—H1	118.5	C17—C18—H18	118.3
C3—C2—C1	118.7 (4)	O4—C19—O3	123.7 (4)
C3—C2—H2	120.7	O4—C19—C20	120.3 (4)
C1—C2—H2	120.7	O3—C19—C20	116.0 (3)
C4—C3—C2	118.8 (4)	C19—C20—H20A	109.5
C4—C3—H3	120.6	C19—C20—H20B	109.5
C2—C3—H3	120.6	H20A—C20—H20B	109.5
C3—C4—C5	119.6 (4)	C19—C20—H20C	109.5
C3—C4—H4	120.2	H20A—C20—H20C	109.5
C5—C4—H4	120.2	H20B—C20—H20C	109.5
N1—C5—C4	122.0 (4)	O6—C21—O5	123.6 (4)
N1—C5—C6	119.3 (3)	O6—C21—C22	120.3 (4)
C4—C5—C6	118.7 (4)	O5—C21—C22	116.1 (4)
O1—C6—C5	109.2 (3)	C21—C22—H22A	109.5
O1—C6—H6A	109.8	C21—C22—H22B	109.5
C5—C6—H6A	109.8	H22A—C22—H22B	109.5
O1—C6—H6B	109.8	C21—C22—H22C	109.5
C5—C6—H6B	109.8	H22A—C22—H22C	109.5
H6A—C6—H6B	108.3	H22B—C22—H22C	109.5
C12—C7—O1	115.3 (3)	O5—Cu1—O3	171.42 (11)
C12—C7—C8	120.8 (4)	O5—Cu1—N1	91.93 (12)
O1—C7—C8	123.9 (4)	O3—Cu1—N1	89.79 (12)
C7—C8—C9	118.9 (5)	O5—Cu1—N2	90.02 (13)
C7—C8—H8	120.5	O3—Cu1—N2	91.66 (13)
C9—C8—H8	120.5	N1—Cu1—N2	157.12 (13)
C10—C9—C8	120.3 (4)	O5—Cu1—O1	86.78 (11)
C10—C9—H9	119.8	O3—Cu1—O1	85.82 (11)
C8—C9—H9	119.8	N1—Cu1—O1	71.06 (11)
C9—C10—C11	120.9 (4)	N2—Cu1—O1	131.82 (11)
C9—C10—H10	119.6	O5—Cu1—O2	86.96 (11)
C11—C10—H10	119.6	O3—Cu1—O2	85.71 (11)
C12—C11—C10	118.9 (5)	N1—Cu1—O2	132.86 (11)
C12—C11—H11	120.6	N2—Cu1—O2	70.01 (11)
C10—C11—H11	120.6	O1—Cu1—O2	61.82 (10)
O2—C12—C7	115.2 (3)	C5—N1—C1	118.0 (3)
O2—C12—C11	124.6 (4)	C5—N1—Cu1	123.7 (2)
C7—C12—C11	120.2 (4)	C1—N1—Cu1	118.3 (3)
O2—C13—C14	108.9 (3)	C18—N2—C14	118.7 (3)
O2—C13—H13	125.6	C18—N2—Cu1	117.0 (3)
C14—C13—H13	125.6	C14—N2—Cu1	124.2 (3)
N2—C14—C15	121.0 (4)	C7—O1—C6	116.5 (3)
N2—C14—C13	119.8 (3)	C7—O1—Cu1	122.2 (2)
C15—C14—C13	119.2 (4)	C6—O1—Cu1	110.1 (2)
C16—C15—C14	119.9 (5)	C12—O2—C13	116.7 (3)
C16—C15—H15	120.0	C12—O2—Cu1	121.9 (2)
C14—C15—H15	120.0	C13—O2—Cu1	110.8 (2)
C15—C16—C17	118.6 (5)	C19—O3—Cu1	115.5 (2)
C15—C16—H16	120.7	C21—O5—Cu1	121.8 (3)
C17—C16—H16	120.7	H60—O7—H61	110.2
C18—C17—C16	118.4 (5)	H62—O8—H63	110.9
C18—C17—H17	120.8	H64—O9—H65	109.5
C16—C17—H17	120.8	H66—O10—H67	109.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H67···O6ⁱ	0.85	2.40	3.072 (6)	137
O10—H66···O9	0.85	2.07	2.913 (6)	169
O9—H64···O8ⁱⁱ	0.85	2.26	2.955 (6)	139
O9—H65···O8	0.85	2.09	2.828 (6)	145
O8—H63···O7ⁱⁱⁱ	0.85	2.06	2.874 (5)	162
O8—H62···O7	0.85	1.94	2.784 (5)	176
O7—H61···O6^iv	0.85	1.91	2.755 (4)	177
O7—H60···O4	0.85	1.94	2.784 (5)	172

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

Experimental details

Crystal data
Chemical formula	[Cu(C₂H₃O₂)₂(C₁₈H₁₆N₂O₂)]·4H₂O
M_r	545.02
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	8.0192 (16), 11.291 (2), 14.117 (3)
α, β, γ (°)	102.97 (3), 92.69 (3), 93.70 (3)
V (Å³)	1240.5 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.94
Crystal size (mm)	0.37 × 0.15 × 0.14

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.726, 0.880
No. of measured, independent and observed [I > 2σ(I)] reflections	12216, 5621, 4677
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.169, 1.05
No. of reflections	5621
No. of parameters	318
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.14, −0.44

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H67···O6ⁱ	0.85	2.40	3.072 (6)	136.8
O10—H66···O9	0.85	2.07	2.913 (6)	169.4
O9—H64···O8ⁱⁱ	0.85	2.26	2.955 (6)	138.8
O9—H65···O8	0.85	2.09	2.828 (6)	145.1
O8—H63···O7ⁱⁱⁱ	0.85	2.06	2.874 (5)	161.6
O8—H62···O7	0.85	1.94	2.784 (5)	176.2
O7—H61···O6^iv	0.85	1.91	2.755 (4)	177.0
O7—H60···O4	0.85	1.94	2.784 (5)	172.3

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

Acknowledgements

The authors thank the Special Funds for the Research of Scientific and Technological Innovative Talents of Harbin Municipal Science and Technology Bureau (2006RFQXG093, 2009RFXXG027), the Science and Technology Planning Project of Heilongjiang Province (GZ08A401) and Heilongjiang University for supporting this study.

References

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
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Zhang, S., Wang, Y.-J., Ma, D.-S., Liu, Y. & Gao, J.-S. (2010). Acta Cryst. E66, m701. Web of Science CSD CrossRef IUCr Journals Google Scholar

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