Bis(1,10-phenanthroline-κ2N,N′)(phenyl­acetato-κO)copper(II) phenyl­acetate hexa­hydrate

Tu, B.-T.; Xie, H.-Z.; Ren, Y.-T.; Chen, J.-Z.

doi:10.1107/S1600536808032480

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1475

doi:10.1107/S1600536808032480

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Bis(1,10-phenanthroline-κ²N,N′)(phenylacetato-κO)copper(II) phenylacetate hexahydrate

Bing-Tian Tu,^a Hong-Zhen Xie,^b ^* Ying-Tao Ren ^a,^b and Jing-Zhong Chen ^a

^aFaculty of Materials Science and Chemical Engineering, China University of Geoscience, Wuhan, Hubei 430074, People's Republic of China, and ^bState Key Laboratory Base of Novel Functional Materials & Preparation Science, Faculty of Materials Science & Chemical Engineering, Institute of Solid Materials Chemistry, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China
^*Correspondence e-mail: zhengyueqing@nbu.edu.cn

(Received 27 August 2008; accepted 8 October 2008; online 31 October 2008)

In the title compound, [Cu(C₈H₇O₂)(C₁₂H₈N₂)₂](C₈H₇O₂)·6H₂O, the Cu atom is in a distorted square-pyramidal coordination environment. The six crystallographically independent uncoordinated water molecules are interconnected by hydrogen bonds, completing dodecawater (H₂O)₁₂ clusters which are hydrogen bonded to the carboxylate groups of phenylacetate anions, building up one-dimensional anionic chains propagating along [100]. Between the cationic and anionic chains are hydrogen bonds from water molecules to the carboxylate O atoms belonging to the phenylacetato ligands.

Related literature

For general background, see: Kuroda-Sowa et al. (1997 ); Lehn (2007 ); Li et al. (2008 ). For related structures, see: Addison & Rao (1984 ); Baruah et al. (2007 ); Liu & Xu (2005 ); Ma et al. (2005 ); Sugimori et al. (1997 ); Zheng et al. (2001 ).

Experimental

Crystal data

[Cu(C₈H₇O₂)(C₁₂H₈N₂)₂](C₈H₇O₂)·6H₂O
M_r = 802.33
Triclinic, $[P \overline 1]$
a = 11.499 (2) Å
b = 11.903 (2) Å
c = 16.066 (3) Å
α = 71.00 (3)°
β = 72.97 (3)°
γ = 68.93 (3)°
V = 1901.3 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 293 (2) K
0.37 × 0.35 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.793, T_max = 0.902
18689 measured reflections
8680 independent reflections
7070 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.095
S = 1.08
8680 reflections
496 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808032480/pk2118sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032480/pk2118Isup2.hkl

checkCIF report

Comment top

Construction of supramolecular architectures with interesting physical properties has grown rapidly owing to their potential use as new functional materials (Lehn, 2007). The most efficient and widely used approach for designing such materials is the self-assembly of organic ligands and metal ions (Kuroda-Sowa et al., 1997; Li et al., 2008). Here, we report a Cu(II) complex [Cu(C₁₂H₈N₂)₂(C₈H₇O₂)](C₈H₇O₂).6H₂O from the self-assembly of Cu(OH)₂, phenylacetatic acid and phenanthroline.

The title compound consists of [Cu(C₁₂H₈N₂)₂(C₈H₇O₂)]²⁺ complex cations, phenylacetate anions, and water molecules of crystallization (Fig.1). The Cu atoms are each coordinated by two phenanthroline ligands and one phenylacetato ligand to complete a square-pyramidal CuN₄O chromophore with the phenylacetic oxygen atom at the equatorial site. The equatorial Cu–N bond lengths fall in the range 2.002–2.060 Å and the Cu–O bond distance is equal to 2.001 (1) Å, while the axial Cu–N bond distance is 2.187 (2) Å. According to Addison's definition (Addison & Rao, 1984), the τ index about the central Cu atom is 0.233 Å, suggesting that the square pyramidal coordination geometry is slightly distorted with the Cu atom deviated from the basal plane by 0.1779 (8) Å towards the apical N1 atom. Within each complex cation, both phenanthroline ligands exhibit nearly perfect coplanarity and constitute an orthogonal system with the coordinating carboxylate group of the phenylacetate anion. The complex cation displays a similar configuration to those observed in a succinato complex [Cu(phen)₂(C₄H₄O₄)] previously reported by us (Zheng et al., 2001) and all the bonding parameters are normal (Baruah et al., 2007). As far as the phenylacetato ligand is concerned, the phenyl plane is found to be nearly perpendicular to the single bonded carbon backbone (dihedral angle: 89.5 (1)°), which is significantly larger than the corresponding one of 68.6 (2)° in the non-coordinating phenylacetate anion, and the carboxylate group is twisted from the single bonded carbon backbone by 70.4 (2)° in the former coordinating one, and is considerably larger the 60.7 (2)° in the non-coordinating anion. As expected, the C–O bond distance for the coordinating oxygen atom is 1.281 (2) Å, which is longer than those for non-coordinating ones (1.247–1.254 Å). The complex cations are distributed in such a way that the symmetry-related phenanthroline ligands are oriented antiparallel with a mean interplanar distance of 3.39 (2) Å, indicating a significant face-to-face π-π stacking interaction (Sugimori et al., 1997). Owing to such intercationic π-π stacking interactions and weak intercationic C–H···O interactions with the uncoordinating carboxylate oxygen atom, two centrosymmetrically related complex cations form dimers, which are further assembled via interdimeric π-π stacking interactions into 1D chains extending along the [101] direction. Furthermore, the resulting chains are arranged in planes parallel to (010), between which the lattice water molecules and the phenylacetate anions are sandwiched.

Out of the six crystallographically distinct lattice water molecules, three water molecules together with their centrosymmetry-related partners are hydrogen bonded to one another to generate chair-like hexawater clusters (Fig.2), to which the remaining lattice water molecules are associated by hydrogen bonds to complete dodecawater (H₂O)₁₂ clusters similar to those reported in the literature (Liu & Xu, 2005; Ma et al., 2005). The resulting dodecawater (H₂O)₁₂ clusters are hydrogen bonded to the carboxylate groups of phenylacetate anions to build up 1D anionic chains propagating along [100]. Between the cationic and anionic chains exist hydrogen bonds from water molecules to the carboxylate oxygen atoms belonging to the phenylacetato ligands.

Related literature top

For general background, see: Kuroda-Sowa et al. (1997); Lehn (2007); Li et al. (2008). For related structures, see: Addison & Rao (1984); Baruah et al. (2007); Liu & Xu (2005); Ma et al. (2005); Sugimori et al. (1997); Zheng et al. (2001).

Experimental top

Dropwise addition of 2.0 mL(1.0 M) of NaOH to a aqueous solution of CuCl₂.2H₂O (0.170 g, 1.00 mmol) in 5.0 mL of H₂O gave a blue precipitate, which was separated by centrifugation and washed with water until no Cl anions were detectable in the supernatant. The collected blue precipitate was transferred to a mixture of ethanol and water (1:1 V/V, 10 mL), to which phenanthroline (0.198 g, 1.00 mmol) and phenylacetic acid (0.136 g, 1.00 mmol) were added successively. The resulting blue solution (pH = 7.52) was allowed to stand at room temperature. Blue blocklike crystals were grown by slow evaporation for over 7 days.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OPTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure and atom labeling scheme of [Cu(C₁₂H₈N₂)₂(C₈H₇O₂)](C₈H₇O₂).6H₂O. H atoms and water molecules are not given. Displacement ellipsoids are drawn at 45%.
	Fig. 2. A chair-like hexawater clusters composed of three water molecules and their centrosymmetry-related parterners is hydrongen bonded.

Bis(1,10-phenanthroline-κ²N,N')(phenylacetato-κO)copper(II) phenylacetate hexahydrate top

Crystal data top

[Cu(C₈H₇O₂)(C₁₂H₈N₂)₂](C₈H₇O₂)·6H₂O	Z = 2
M_r = 802.33	F(000) = 838
Triclinic, P1	D_x = 1.401 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.499 (2) Å	Cell parameters from 14647 reflections
b = 11.903 (2) Å	θ = 3.0–27.5°
c = 16.066 (3) Å	µ = 0.64 mm⁻¹
α = 71.00 (3)°	T = 293 K
β = 72.97 (3)°	Prism, blue
γ = 68.93 (3)°	0.37 × 0.35 × 0.17 mm
V = 1901.3 (8) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	8680 independent reflections
Radiation source: fine-focus sealed tube	7070 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→14
T_min = 0.793, T_max = 0.902	k = −15→15
18689 measured reflections	l = −20→20

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0351P)² + 1.3044P] where P = (F_o² + 2F_c²)/3
8680 reflections	(Δ/σ)_max = 0.002
496 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Cu(C₈H₇O₂)(C₁₂H₈N₂)₂](C₈H₇O₂)·6H₂O	γ = 68.93 (3)°
M_r = 802.33	V = 1901.3 (8) Å³
Triclinic, P1	Z = 2
a = 11.499 (2) Å	Mo Kα radiation
b = 11.903 (2) Å	µ = 0.64 mm⁻¹
c = 16.066 (3) Å	T = 293 K
α = 71.00 (3)°	0.37 × 0.35 × 0.17 mm
β = 72.97 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	8680 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	7070 reflections with I > 2σ(I)
T_min = 0.793, T_max = 0.902	R_int = 0.030
18689 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.08	Δρ_max = 0.41 e Å⁻³
8680 reflections	Δρ_min = −0.39 e Å⁻³
496 parameters

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
Cu	0.68956 (2)	0.48613 (2)	0.746890 (15)	0.01698 (7)
N1	0.88512 (16)	0.37869 (15)	0.70294 (11)	0.0202 (3)
N2	0.75896 (16)	0.62363 (15)	0.66308 (10)	0.0187 (3)
C1	0.9447 (2)	0.25741 (19)	0.72006 (14)	0.0246 (4)
H1A	0.8995	0.2027	0.7579	0.030*
C2	1.0735 (2)	0.2091 (2)	0.68296 (15)	0.0299 (5)
H2A	1.1123	0.1238	0.6966	0.036*
C3	1.1417 (2)	0.2876 (2)	0.62679 (14)	0.0282 (5)
H3A	1.2272	0.2565	0.6024	0.034*
C4	1.08088 (19)	0.4164 (2)	0.60633 (13)	0.0234 (4)
C5	1.1439 (2)	0.5061 (2)	0.54605 (13)	0.0263 (5)
H5A	1.2291	0.4792	0.5192	0.032*
C6	1.0814 (2)	0.6284 (2)	0.52797 (13)	0.0274 (5)
H6A	1.1245	0.6846	0.4893	0.033*
C7	0.9498 (2)	0.6735 (2)	0.56728 (12)	0.0223 (4)
C8	0.8792 (2)	0.7998 (2)	0.54857 (13)	0.0265 (5)
H8A	0.9184	0.8592	0.5104	0.032*
C9	0.7529 (2)	0.8349 (2)	0.58661 (14)	0.0265 (5)
H9A	0.7059	0.9183	0.5749	0.032*
C10	0.6947 (2)	0.74424 (19)	0.64352 (13)	0.0228 (4)
H10A	0.6084	0.7689	0.6685	0.027*
C11	0.88530 (19)	0.58773 (19)	0.62585 (12)	0.0190 (4)
C12	0.95214 (19)	0.45701 (19)	0.64659 (12)	0.0192 (4)
N3	0.71006 (15)	0.52113 (15)	0.85842 (10)	0.0184 (3)
N4	0.61981 (15)	0.35480 (15)	0.84204 (10)	0.0179 (3)
C13	0.75535 (19)	0.60510 (19)	0.86524 (14)	0.0234 (4)
H13A	0.7805	0.6612	0.8131	0.028*
C14	0.7671 (2)	0.6132 (2)	0.94739 (15)	0.0276 (5)
H14A	0.8004	0.6728	0.9491	0.033*
C15	0.7289 (2)	0.5323 (2)	1.02531 (14)	0.0267 (5)
H15A	0.7355	0.5369	1.0804	0.032*
C16	0.67958 (19)	0.44215 (19)	1.02106 (13)	0.0215 (4)
C17	0.6358 (2)	0.3548 (2)	1.09815 (13)	0.0255 (4)
H17A	0.6405	0.3554	1.1548	0.031*
C18	0.5875 (2)	0.2709 (2)	1.09022 (13)	0.0253 (4)
H18A	0.5588	0.2156	1.1415	0.030*
C19	0.57996 (18)	0.26646 (18)	1.00364 (13)	0.0204 (4)
C20	0.53024 (19)	0.18274 (18)	0.99020 (13)	0.0236 (4)
H20A	0.4996	0.1256	1.0390	0.028*
C21	0.5275 (2)	0.18630 (19)	0.90460 (14)	0.0241 (4)
H21A	0.4949	0.1316	0.8949	0.029*
C22	0.57429 (19)	0.27314 (18)	0.83178 (13)	0.0219 (4)
H22A	0.5734	0.2736	0.7740	0.026*
C23	0.62315 (17)	0.35128 (17)	0.92720 (12)	0.0169 (4)
C24	0.67262 (18)	0.44035 (18)	0.93590 (12)	0.0180 (4)
O1	0.60569 (13)	0.47269 (12)	0.65901 (9)	0.0194 (3)
O2	0.46263 (13)	0.63541 (13)	0.70364 (9)	0.0227 (3)
C25	0.49547 (18)	0.55256 (18)	0.66273 (12)	0.0178 (4)
C26	0.40023 (19)	0.53846 (19)	0.62087 (12)	0.0196 (4)
H26A	0.3618	0.6176	0.5828	0.024*
H26B	0.4432	0.4792	0.5841	0.024*
C27	0.29830 (18)	0.49355 (18)	0.69518 (12)	0.0184 (4)
C28	0.19012 (19)	0.57800 (19)	0.72970 (13)	0.0223 (4)
H28A	0.1794	0.6628	0.7065	0.027*
C29	0.0977 (2)	0.5369 (2)	0.79870 (14)	0.0267 (4)
H29A	0.0255	0.5944	0.8212	0.032*
C30	0.1120 (2)	0.4103 (2)	0.83452 (14)	0.0271 (5)
H30A	0.0501	0.3828	0.8808	0.033*
C31	0.2201 (2)	0.3260 (2)	0.79992 (14)	0.0269 (5)
H31A	0.2306	0.2412	0.8232	0.032*
C32	0.3130 (2)	0.36672 (19)	0.73082 (13)	0.0226 (4)
H32A	0.3851	0.3092	0.7083	0.027*
O3	0.92255 (14)	0.04315 (14)	0.61308 (10)	0.0298 (3)
O4	0.74454 (15)	0.07607 (14)	0.71534 (10)	0.0311 (4)
C33	0.8540 (2)	0.01148 (18)	0.68752 (14)	0.0239 (4)
C34	0.9041 (3)	−0.1168 (2)	0.74904 (15)	0.0358 (6)
H34A	0.8474	−0.1657	0.7587	0.043*
H34B	0.9869	−0.1587	0.7186	0.043*
C35	0.9159 (2)	−0.11314 (18)	0.83942 (15)	0.0283 (5)
C36	1.0334 (2)	−0.1482 (2)	0.86166 (17)	0.0370 (6)
H36A	1.1067	−0.1717	0.8196	0.044*
C37	1.0441 (2)	−0.1489 (2)	0.94604 (19)	0.0414 (6)
H37A	1.1241	−0.1726	0.9597	0.050*
C38	0.9367 (2)	−0.1145 (2)	1.00936 (17)	0.0343 (5)
H38A	0.9438	−0.1161	1.0660	0.041*
C39	0.8190 (2)	−0.0779 (2)	0.98804 (15)	0.0320 (5)
H39A	0.7462	−0.0532	1.0301	0.038*
C40	0.8079 (2)	−0.0776 (2)	0.90389 (15)	0.0299 (5)
H40A	0.7277	−0.0535	0.8905	0.036*
O5	0.39349 (18)	1.03378 (16)	0.68444 (12)	0.0399 (4)
H5B	0.3819	0.9842	0.6619	0.048*
H5C	0.4245	1.0861	0.6352	0.048*
O6	0.35322 (16)	0.87072 (14)	0.61361 (12)	0.0356 (4)
H6B	0.3705	0.7956	0.6428	0.043*
H6C	0.2684	0.8806	0.6087	0.043*
O7	1.14845 (15)	−0.11805 (14)	0.55998 (10)	0.0307 (3)
H7B	1.0657	−0.0635	0.5770	0.037*
H7C	1.1480	−0.1006	0.5005	0.037*
O8	0.52945 (16)	0.78513 (16)	0.46170 (11)	0.0351 (4)
H8B	0.4871	0.8222	0.5025	0.042*
H8C	0.4789	0.7740	0.4378	0.042*
O9	0.54855 (19)	−0.03208 (19)	0.80451 (11)	0.0478 (5)
H9B	0.5011	−0.0164	0.7692	0.057*
H9C	0.6005	−0.0017	0.7841	0.057*
O10	0.64854 (14)	0.27146 (13)	0.58757 (9)	0.0261 (3)
H10B	0.6377	0.3379	0.6076	0.031*
H10C	0.6953	0.2065	0.6203	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.01848 (13)	0.01903 (12)	0.01421 (11)	−0.01010 (9)	−0.00353 (9)	0.00032 (9)
N1	0.0194 (8)	0.0230 (8)	0.0198 (8)	−0.0072 (7)	−0.0056 (7)	−0.0048 (7)
N2	0.0204 (8)	0.0226 (8)	0.0146 (7)	−0.0111 (7)	−0.0037 (6)	−0.0010 (7)
C1	0.0251 (11)	0.0232 (10)	0.0267 (10)	−0.0075 (9)	−0.0077 (9)	−0.0048 (9)
C2	0.0268 (11)	0.0281 (11)	0.0364 (12)	−0.0003 (9)	−0.0133 (10)	−0.0123 (10)
C3	0.0190 (10)	0.0410 (13)	0.0285 (11)	−0.0049 (9)	−0.0070 (9)	−0.0158 (10)
C4	0.0196 (10)	0.0378 (12)	0.0194 (9)	−0.0108 (9)	−0.0043 (8)	−0.0127 (9)
C5	0.0195 (10)	0.0486 (14)	0.0180 (9)	−0.0175 (10)	−0.0001 (8)	−0.0123 (10)
C6	0.0274 (11)	0.0469 (13)	0.0165 (9)	−0.0255 (10)	−0.0008 (8)	−0.0057 (9)
C7	0.0266 (11)	0.0336 (11)	0.0131 (8)	−0.0187 (9)	−0.0036 (8)	−0.0032 (8)
C8	0.0375 (12)	0.0311 (11)	0.0178 (9)	−0.0242 (10)	−0.0061 (9)	0.0015 (9)
C9	0.0346 (12)	0.0238 (10)	0.0233 (10)	−0.0147 (9)	−0.0096 (9)	0.0017 (9)
C10	0.0252 (11)	0.0233 (10)	0.0206 (9)	−0.0105 (8)	−0.0060 (8)	−0.0013 (8)
C11	0.0214 (10)	0.0280 (10)	0.0126 (8)	−0.0123 (8)	−0.0046 (7)	−0.0048 (8)
C12	0.0202 (10)	0.0272 (10)	0.0145 (8)	−0.0106 (8)	−0.0047 (7)	−0.0054 (8)
N3	0.0163 (8)	0.0219 (8)	0.0181 (8)	−0.0073 (7)	−0.0038 (6)	−0.0039 (7)
N4	0.0175 (8)	0.0192 (8)	0.0169 (7)	−0.0076 (7)	−0.0032 (6)	−0.0018 (7)
C13	0.0219 (10)	0.0255 (10)	0.0235 (10)	−0.0113 (8)	−0.0045 (8)	−0.0022 (9)
C14	0.0246 (11)	0.0327 (11)	0.0336 (11)	−0.0123 (9)	−0.0065 (9)	−0.0137 (10)
C15	0.0223 (11)	0.0344 (12)	0.0261 (10)	−0.0031 (9)	−0.0073 (9)	−0.0145 (10)
C16	0.0161 (9)	0.0265 (10)	0.0183 (9)	−0.0016 (8)	−0.0026 (7)	−0.0067 (8)
C17	0.0234 (11)	0.0313 (11)	0.0159 (9)	−0.0018 (9)	−0.0042 (8)	−0.0048 (9)
C18	0.0226 (10)	0.0280 (11)	0.0161 (9)	−0.0039 (9)	−0.0012 (8)	0.0001 (8)
C19	0.0161 (9)	0.0205 (9)	0.0172 (9)	−0.0027 (8)	−0.0012 (7)	−0.0001 (8)
C20	0.0210 (10)	0.0187 (9)	0.0222 (10)	−0.0065 (8)	−0.0009 (8)	0.0040 (8)
C21	0.0236 (11)	0.0204 (10)	0.0282 (10)	−0.0101 (8)	−0.0054 (9)	−0.0017 (9)
C22	0.0227 (10)	0.0236 (10)	0.0205 (9)	−0.0090 (8)	−0.0046 (8)	−0.0039 (8)
C23	0.0131 (9)	0.0184 (9)	0.0148 (8)	−0.0026 (7)	−0.0025 (7)	−0.0012 (7)
C24	0.0132 (9)	0.0201 (9)	0.0174 (9)	−0.0015 (7)	−0.0035 (7)	−0.0038 (8)
O1	0.0204 (7)	0.0212 (7)	0.0170 (6)	−0.0089 (6)	−0.0052 (5)	−0.0010 (6)
O2	0.0237 (7)	0.0284 (7)	0.0179 (6)	−0.0100 (6)	−0.0019 (6)	−0.0076 (6)
C25	0.0195 (10)	0.0213 (9)	0.0107 (8)	−0.0101 (8)	−0.0012 (7)	0.0016 (7)
C26	0.0199 (10)	0.0236 (10)	0.0155 (9)	−0.0066 (8)	−0.0056 (7)	−0.0030 (8)
C27	0.0194 (10)	0.0228 (9)	0.0162 (8)	−0.0084 (8)	−0.0084 (7)	−0.0019 (8)
C28	0.0211 (10)	0.0230 (10)	0.0231 (10)	−0.0075 (8)	−0.0059 (8)	−0.0034 (8)
C29	0.0183 (10)	0.0347 (12)	0.0275 (10)	−0.0077 (9)	−0.0032 (8)	−0.0095 (9)
C30	0.0255 (11)	0.0383 (12)	0.0211 (10)	−0.0202 (10)	−0.0038 (8)	−0.0007 (9)
C31	0.0356 (12)	0.0244 (10)	0.0251 (10)	−0.0168 (9)	−0.0131 (9)	0.0034 (9)
C32	0.0239 (10)	0.0225 (10)	0.0229 (10)	−0.0058 (8)	−0.0089 (8)	−0.0048 (8)
O3	0.0261 (8)	0.0244 (8)	0.0299 (8)	−0.0068 (6)	−0.0034 (6)	0.0023 (7)
O4	0.0313 (9)	0.0238 (8)	0.0272 (8)	−0.0068 (7)	−0.0010 (7)	0.0023 (6)
C33	0.0302 (11)	0.0166 (9)	0.0239 (10)	−0.0085 (9)	−0.0076 (9)	−0.0001 (8)
C34	0.0529 (16)	0.0179 (10)	0.0274 (11)	−0.0038 (10)	−0.0079 (11)	−0.0012 (9)
C35	0.0354 (12)	0.0139 (9)	0.0286 (11)	−0.0048 (9)	−0.0056 (9)	0.0006 (9)
C36	0.0304 (13)	0.0282 (12)	0.0446 (14)	−0.0035 (10)	−0.0012 (11)	−0.0101 (11)
C37	0.0309 (13)	0.0395 (14)	0.0561 (16)	−0.0032 (11)	−0.0164 (12)	−0.0156 (13)
C38	0.0400 (14)	0.0268 (11)	0.0363 (12)	−0.0072 (10)	−0.0150 (11)	−0.0041 (10)
C39	0.0330 (12)	0.0288 (11)	0.0256 (11)	−0.0069 (10)	−0.0035 (9)	−0.0002 (9)
C40	0.0274 (11)	0.0268 (11)	0.0275 (11)	−0.0052 (9)	−0.0078 (9)	0.0026 (9)
O5	0.0506 (11)	0.0361 (9)	0.0412 (9)	−0.0205 (8)	−0.0180 (8)	−0.0034 (8)
O6	0.0385 (9)	0.0259 (8)	0.0460 (10)	−0.0092 (7)	−0.0167 (8)	−0.0065 (7)
O7	0.0279 (8)	0.0314 (8)	0.0277 (8)	−0.0047 (7)	−0.0064 (6)	−0.0044 (7)
O8	0.0335 (9)	0.0430 (10)	0.0340 (8)	−0.0173 (8)	−0.0045 (7)	−0.0114 (8)
O9	0.0638 (13)	0.0678 (13)	0.0242 (8)	−0.0491 (11)	−0.0145 (8)	0.0113 (8)
O10	0.0317 (8)	0.0221 (7)	0.0245 (7)	−0.0073 (6)	−0.0095 (6)	−0.0031 (6)

Geometric parameters (Å, º) top

Cu—N2	2.0009 (18)	C21—H21A	0.9300
Cu—O1	2.0011 (14)	C22—H22A	0.9300
Cu—N4	2.0128 (17)	C23—C24	1.430 (3)
Cu—N3	2.0600 (16)	O1—C25	1.281 (2)
Cu—N1	2.1866 (19)	O2—C25	1.247 (2)
N1—C1	1.330 (3)	C25—C26	1.522 (3)
N1—C12	1.357 (3)	C26—C27	1.517 (3)
N2—C10	1.336 (3)	C26—H26A	0.9700
N2—C11	1.365 (3)	C26—H26B	0.9700
C1—C2	1.405 (3)	C27—C28	1.388 (3)
C1—H1A	0.9300	C27—C32	1.395 (3)
C2—C3	1.366 (3)	C28—C29	1.389 (3)
C2—H2A	0.9300	C28—H28A	0.9300
C3—C4	1.408 (3)	C29—C30	1.393 (3)
C3—H3A	0.9300	C29—H29A	0.9300
C4—C12	1.404 (3)	C30—C31	1.387 (3)
C4—C5	1.441 (3)	C30—H30A	0.9300
C5—C6	1.347 (3)	C31—C32	1.391 (3)
C5—H5A	0.9300	C31—H31A	0.9300
C6—C7	1.434 (3)	C32—H32A	0.9300
C6—H6A	0.9300	O3—C33	1.250 (3)
C7—C8	1.407 (3)	O4—C33	1.254 (3)
C7—C11	1.410 (3)	C33—C34	1.536 (3)
C8—C9	1.366 (3)	C34—C35	1.513 (3)
C8—H8A	0.9300	C34—H34A	0.9700
C9—C10	1.403 (3)	C34—H34B	0.9700
C9—H9A	0.9300	C35—C36	1.382 (3)
C10—H10A	0.9300	C35—C40	1.395 (3)
C11—C12	1.441 (3)	C36—C37	1.394 (4)
N3—C13	1.327 (3)	C36—H36A	0.9300
N3—C24	1.365 (3)	C37—C38	1.378 (4)
N4—C22	1.329 (2)	C37—H37A	0.9300
N4—C23	1.367 (2)	C38—C39	1.375 (3)
C13—C14	1.402 (3)	C38—H38A	0.9300
C13—H13A	0.9300	C39—C40	1.393 (3)
C14—C15	1.373 (3)	C39—H39A	0.9300
C14—H14A	0.9300	C40—H40A	0.9300
C15—C16	1.409 (3)	O5—H5B	0.8492
C15—H15A	0.9300	O5—H5C	0.9025
C16—C24	1.401 (3)	O6—H6B	0.8443
C16—C17	1.429 (3)	O6—H6C	0.9634
C17—C18	1.359 (3)	O7—H7B	0.9596
C17—H17A	0.9300	O7—H7C	0.9107
C18—C19	1.438 (3)	O8—H8B	0.8418
C18—H18A	0.9300	O8—H8C	0.8508
C19—C23	1.404 (3)	O9—H9B	0.8328
C19—C20	1.410 (3)	O9—H9C	0.7473
C20—C21	1.371 (3)	O10—H10B	0.9033
C20—H20A	0.9300	O10—H10C	0.8749
C21—C22	1.404 (3)

N2—Cu—O1	95.38 (6)	C20—C19—C18	124.14 (18)
N2—Cu—N4	173.84 (6)	C21—C20—C19	119.44 (18)
O1—Cu—N4	90.11 (6)	C21—C20—H20A	120.3
N2—Cu—N3	92.59 (7)	C19—C20—H20A	120.3
O1—Cu—N3	159.85 (6)	C20—C21—C22	119.49 (19)
N4—Cu—N3	81.31 (7)	C20—C21—H21A	120.3
N2—Cu—N1	80.25 (7)	C22—C21—H21A	120.3
O1—Cu—N1	99.99 (6)	N4—C22—C21	122.70 (18)
N4—Cu—N1	101.58 (7)	N4—C22—H22A	118.7
N3—Cu—N1	99.58 (7)	C21—C22—H22A	118.7
C1—N1—C12	118.02 (18)	N4—C23—C19	123.02 (18)
C1—N1—Cu	132.56 (14)	N4—C23—C24	116.59 (16)
C12—N1—Cu	109.42 (13)	C19—C23—C24	120.39 (17)
C10—N2—C11	118.72 (17)	N3—C24—C16	123.45 (18)
C10—N2—Cu	126.25 (14)	N3—C24—C23	116.65 (17)
C11—N2—Cu	114.99 (13)	C16—C24—C23	119.90 (18)
N1—C1—C2	122.3 (2)	C25—O1—Cu	108.11 (12)
N1—C1—H1A	118.8	O2—C25—O1	122.11 (18)
C2—C1—H1A	118.8	O2—C25—C26	119.94 (18)
C3—C2—C1	119.9 (2)	O1—C25—C26	117.82 (17)
C3—C2—H2A	120.1	C27—C26—C25	108.99 (15)
C1—C2—H2A	120.1	C27—C26—H26A	109.9
C2—C3—C4	119.2 (2)	C25—C26—H26A	109.9
C2—C3—H3A	120.4	C27—C26—H26B	109.9
C4—C3—H3A	120.4	C25—C26—H26B	109.9
C12—C4—C3	117.3 (2)	H26A—C26—H26B	108.3
C12—C4—C5	119.5 (2)	C28—C27—C32	119.05 (19)
C3—C4—C5	123.19 (19)	C28—C27—C26	120.48 (18)
C6—C5—C4	121.05 (19)	C32—C27—C26	120.47 (18)
C6—C5—H5A	119.5	C27—C28—C29	120.5 (2)
C4—C5—H5A	119.5	C27—C28—H28A	119.8
C5—C6—C7	121.2 (2)	C29—C28—H28A	119.8
C5—C6—H6A	119.4	C28—C29—C30	120.6 (2)
C7—C6—H6A	119.4	C28—C29—H29A	119.7
C8—C7—C11	117.52 (19)	C30—C29—H29A	119.7
C8—C7—C6	123.42 (19)	C31—C30—C29	118.83 (19)
C11—C7—C6	119.0 (2)	C31—C30—H30A	120.6
C9—C8—C7	119.88 (19)	C29—C30—H30A	120.6
C9—C8—H8A	120.1	C30—C31—C32	120.7 (2)
C7—C8—H8A	120.1	C30—C31—H31A	119.6
C8—C9—C10	119.5 (2)	C32—C31—H31A	119.6
C8—C9—H9A	120.3	C31—C32—C27	120.3 (2)
C10—C9—H9A	120.3	C31—C32—H32A	119.9
N2—C10—C9	122.2 (2)	C27—C32—H32A	119.9
N2—C10—H10A	118.9	O3—C33—O4	124.60 (19)
C9—C10—H10A	118.9	O3—C33—C34	118.50 (19)
N2—C11—C7	122.18 (19)	O4—C33—C34	116.88 (19)
N2—C11—C12	117.75 (17)	C35—C34—C33	114.35 (18)
C7—C11—C12	120.06 (18)	C35—C34—H34A	108.7
N1—C12—C4	123.28 (19)	C33—C34—H34A	108.7
N1—C12—C11	117.49 (17)	C35—C34—H34B	108.7
C4—C12—C11	119.20 (18)	C33—C34—H34B	108.7
C13—N3—C24	117.51 (17)	H34A—C34—H34B	107.6
C13—N3—Cu	130.54 (14)	C36—C35—C40	118.0 (2)
C24—N3—Cu	111.93 (12)	C36—C35—C34	121.2 (2)
C22—N4—C23	118.00 (17)	C40—C35—C34	120.9 (2)
C22—N4—Cu	128.52 (13)	C35—C36—C37	121.2 (2)
C23—N4—Cu	113.47 (12)	C35—C36—H36A	119.4
N3—C13—C14	123.11 (19)	C37—C36—H36A	119.4
N3—C13—H13A	118.4	C38—C37—C36	120.3 (2)
C14—C13—H13A	118.4	C38—C37—H37A	119.8
C15—C14—C13	119.33 (19)	C36—C37—H37A	119.8
C15—C14—H14A	120.3	C39—C38—C37	119.4 (2)
C13—C14—H14A	120.3	C39—C38—H38A	120.3
C14—C15—C16	119.35 (19)	C37—C38—H38A	120.3
C14—C15—H15A	120.3	C38—C39—C40	120.5 (2)
C16—C15—H15A	120.3	C38—C39—H39A	119.8
C24—C16—C15	117.25 (19)	C40—C39—H39A	119.8
C24—C16—C17	119.03 (19)	C39—C40—C35	120.8 (2)
C15—C16—C17	123.72 (19)	C39—C40—H40A	119.6
C18—C17—C16	121.23 (19)	C35—C40—H40A	119.6
C18—C17—H17A	119.4	H5B—O5—H5C	102.2
C16—C17—H17A	119.4	H6B—O6—H6C	97.9
C17—C18—C19	120.92 (19)	H7B—O7—H7C	97.3
C17—C18—H18A	119.5	H8B—O8—H8C	109.3
C19—C18—H18A	119.5	H9B—O9—H9C	112.4
C23—C19—C20	117.33 (18)	H10B—O10—H10C	107.4
C23—C19—C18	118.53 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O6	0.849	1.920	2.769 (3)	178.64
O5—H5C···O8ⁱ	0.902	1.898	2.794 (3)	171.66
O6—H6B···O2	0.844	1.912	2.723 (2)	160.78
O6—H6C···O7ⁱⁱ	0.963	1.767	2.682 (3)	157.25
O7—H7B···O3	0.960	1.754	2.710 (2)	173.79
O7—H7C···O3ⁱⁱⁱ	0.911	2.028	2.896 (2)	158.83
O8—H8B···O6	0.842	2.076	2.888 (3)	161.67
O8—H8C···O10^iv	0.851	1.915	2.749 (3)	166.41
O9—H9B···O5^v	0.833	1.915	2.746 (3)	175.07
O9—H9C···O4	0.747	2.046	2.790 (3)	173.58
O10—H10B···O1	0.903	1.911	2.812 (2)	175.12
O10—H10C···O4	0.875	1.842	2.686 (2)	161.44

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

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₇O₂)(C₁₂H₈N₂)₂](C₈H₇O₂)·6H₂O
M_r	802.33
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	11.499 (2), 11.903 (2), 16.066 (3)
α, β, γ (°)	71.00 (3), 72.97 (3), 68.93 (3)
V (Å³)	1901.3 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.37 × 0.35 × 0.17

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.793, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	18689, 8680, 7070
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.095, 1.08
No. of reflections	8680
No. of parameters	496
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.39

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OPTEPII (Johnson, 1976).

Acknowledgements

This project was sponsored by the K. C. Wong Magna Fund of Ningbo University and supported by the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Zhejiang Provincial Natural Science Foundation (grant No. Z203067) and the Ningbo Municipal Natural Science Foundation (grant No. 2006 A610061).

References

Addison, A. W. & Rao, N. T. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1984. CSD CrossRef Web of Science Google Scholar
Baruah, A. M., Karmaker, A. & Baruah, J. B. (2007). Polyhedron, 26, 4479–4488. Web of Science CSD CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Kuroda-Sowa, T., Horino, T., Yamamoto, M., Ohno, Y., Maekawa, M. & Munakata, M. (1997). Inorg. Chem. 36, 6382–6389. Web of Science CSD CrossRef CAS Google Scholar
Lehn, J. M. (2007). Chem. Rev. 36, 151–160. CrossRef CAS Google Scholar
Li, X., Cheng, D. Y., Li, Z. F. & Zheng, Y. Q. (2008). Cryst. Growth Des. 8, 2853–2861. Web of Science CSD CrossRef CAS Google Scholar
Liu, Q. Y. & Xu, L. (2005). CrystEngComm, 7, 87–89. Web of Science CSD CrossRef CAS Google Scholar
Ma, B. Q., Sun, H. L. & Gao, S. (2005). Chem. Commun. pp. 2336–2338. Web of Science CSD CrossRef Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sugimori, T., Masuda, H., Ohata, N., Koiwai, K., Odani, A. & Yamauchi, O. (1997). Inorg. Chem. 36, 576–583. CSD CrossRef CAS Web of Science Google Scholar
Zheng, Y. Q., Sun, J. & Lin, J. L. (2001). Z. Anorg. Allg. Chem. 627, 90–94. Web of Science CSD CrossRef CAS Google Scholar

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