(Benzoato-κO)bis­(1,10-phenanthroline-κ2N,N′)copper(II) chloride benzoic acid disolvate

Huang, W.-X.; Liu, B.-B.; Lin, J.-L.

doi:10.1107/S1600536810011487

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Pages m488-m489

https://doi.org/10.1107/S1600536810011487

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(Benzoato-κO)bis(1,10-phenanthroline-κ²N,N′)copper(II) chloride benzoic acid disolvate

Wen-Xiang Huang,^a Bin-Bin Liu ^a and Jian-Li Lin ^a ^*

^aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Center of Applied Solid State Chemistry Research, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China
^*Correspondence e-mail: linjianli@nbu.edu.cn

(Received 12 March 2010; accepted 26 March 2010; online 2 April 2010)

In the title complex, [Cu(C₇H₅O₂)(C₁₂H₈N₂)₂]Cl·2C₆H₅COOH, the Cu^II ion is coordinated by one carboxylate O atom from a benzoate anion and four N atoms from two phenantroline ligands in a distorted five-coordinate trigonal-bipyramidal CuON₄ chromophore. The Cu²⁺ and the Cl⁻ ion are imposed by a twofold rotation axiss which also bisects the equally disordered benzoate anion. In the crystal, the molecules are assembled into chains along [010] by C—H⋯Cl, O—H⋯Cl and C—H⋯O hydrogen-bonding interactions. The resulting chains are further connected into two-dimensional supramolecular layers parallel to [100] by interchain π⋯π stacking interactions [centroid–centroid distance = 3.823 (5) Å] between the phenanthroline ligands and the benzoic acid molecules, and by C—H⋯O hydrogen-bonding interactions. Strong π⋯π stacking interactions between adjacent phenantroline ligands [3.548 (4) Å] assemble the layers into a three-dimensional supramolecular architecture.

Related literature

For copper–aromatic acid coordination polymers, see: Li et al. (2006 ); Devereux et al. (2007 ). For related structures, see: Mao et al. (2001 ). For the τ parameter, see: Addison et al. (1984 ).

Experimental

Crystal data

[Cu(C₇H₅O₂)(C₁₂H₈N₂)₂]Cl·2C₇H₆O₂
M_r = 824.74
Monoclinic, C 2/c
a = 16.724 (3) Å
b = 19.288 (4) Å
c = 13.295 (3) Å
β = 113.86 (3)°
V = 3922.1 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 293 K
0.35 × 0.31 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.710, T_max = 0.750
15193 measured reflections
3449 independent reflections
2623 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.101
S = 1.08
3449 reflections
286 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯Cl	0.96	2.94	3.728 (4)	140
O3—H31⋯Cl	0.85 (4)	2.20 (4)	3.051 (3)	177 (4)
O3—H31⋯Clⁱ	0.85 (4)	2.20 (4)	3.051 (3)	177 (4)
C24—H24A⋯O4ⁱⁱ	0.93	2.49	3.355 (5)	155
C8—H8A⋯O3ⁱⁱⁱ	0.93	2.47	3.307 (4)	149
C10—H10A⋯O1^iv	0.93	2.53	3.275 (7)	138
C12—H12A⋯O1^iv	0.93	2.30	3.106 (7)	146
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+2, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); 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: https://doi.org/10.1107/S1600536810011487/zq2032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810011487/zq2032Isup2.hkl

checkCIF report

Comment top

Over the past decades, vast efforts have been dedicated to rational design and synthesis of copper-aromatic-acid coordination polymers, due to their potential applications in medicine, electronics, magnetism, catalysis, gas storage, etc··· It is well known that aromatic carboxylic acids, such as p–phthalic acid (Li et al., 2006) and salicylic acid (Devereux et al., 2007), were used to construct coordination polymers with copper salts and exhibited interesting electrochemical properties. In the present contribution, we report a new copper coordination complex, [Cu(phen)₂(C₆H₅COO)].2(C₆H₅COOH).Cl, resulting from self-assembly of Cu^II ions, phenanthroline ligands and benzoic acid molecules.

The crystal structure of the title complex consists of [Cu(phen)₂(C₆H₅COO)]⁺cations, free benzoic acid molecules and uncoordinated Cl^– anions in a ratio 1:2:1. The Cu^II ion is coordinated by one carboxylate O atom from a benzoate anion and four N atoms from two phenantroline ligands to complete a distorted five–coordinate trigonal bipyramidal CuON₄ chromophore. The equatorial positions of the Cu^II ion are occupied by one O atom and two N atoms from different phen molecules, and the axial ones by the other two N atoms. The Addison's τ value of 0.53 (τ = 0 for an ideal square pyramid and τ = 1 for an ideal trigonal bipyramid) speaks for a trigonal bipyramid character with a '3+2' coordination type (Addison et al., 1984), which is similar to that of Cu atom in the literature (Mao et al., 2001). The dihedral angle between the benzene ring plane and the carboxylate plane of the coordinated benzoic ion is 14.4 (1)°, which is larger than the dihedral angle in the free benzoic acid molecule (6.5 (6)°). In addition, the Cu^II ions and the benzoate ligands are crystallographically imposed by 2–fold rotation axes. The molecules are assembled into one-dimensional chains along [010] direction through hydrogen bonds interactions (C5–H5A···Cl, O3–H3A···Cl, C24–H24A···O4, C8–H8A···O3). The resulting chains are further connected into two-dimensional supramolecular layers parallel to [100] by interchain π···π stacking interactions (3.823 (5) Å) between the phenantroline ligands and the molecular benzoic acid, and by hydrogen bonding interactions (C10–H10A···O1, C12–H12A···O1). Furthermore, on the basis of strong π···π stacking interactions between interlayer adjacent phenantroline ligands (3.548 (4) Å), the layers are assembled into a three-dimensional supramolecular architecture.

Related literature top

For copper–aromatic acid coordination polymers, see: Li et al. (2006); Devereux et al. (2007). For related structures, see: Mao et al. (2001). For the τ parameter, see: Addison et al. (1984).

Experimental top

Dropwise addition of 2.0 mL (1.0 M) NaOH to a stirred aqueous solution of 0.1708 g (1.001 mmol) CuCl₂.H₂O in 10.0 mL H₂O afforded a blue precipitate, which was separated by centrifugation and washed with distilled water for 5 times. The gathered precipitate was then transferred into a solution of benzoic acid (0.2448 g, 2.0049 mmol) and 1,10-phenanthroline (0.1986 g, 1.002 mmol) in a mixed solvent composed of 10.0 mL H₂O and 10.0 mL ethanol to yield a blue suspension. The mixture was then stirred for further 30 min. After filtration, the filtrate was kept at room temperature and afforded a small amount of blue crystalline blocks after 20 days.

Structure description top

For copper–aromatic acid coordination polymers, see: Li et al. (2006); Devereux et al. (2007). For related structures, see: Mao et al. (2001). For the τ parameter, see: Addison et al. (1984).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP view of the title compound. The displacement ellipsoids are drawn at the 20% probability level.
	Fig. 2. The three-dimensional structure of the title complex through π···π stacking and hydrogen bond interactions.

(Benzoato-κO)bis(1,10-phenanthroline-κ²N,N')copper(II) chloride benzoic acid disolvate top

Crystal data top

[Cu(C₇H₅O₂)(C₁₂H₈N₂)₂]Cl·2C₇H₆O₂	F(000) = 1700
M_r = 824.74	D_x = 1.397 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 15193 reflections
a = 16.724 (3) Å	θ = 3.2–25.0°
b = 19.288 (4) Å	µ = 0.68 mm⁻¹
c = 13.295 (3) Å	T = 293 K
β = 113.86 (3)°	Block, blue
V = 3922.1 (14) Å³	0.35 × 0.31 × 0.28 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	3449 independent reflections
Radiation source: fine-focus sealed tube	2623 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 0 pixels mm^-1	θ_max = 25.0°, θ_min = 3.2°
ω scans	h = −19→17
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −22→22
T_min = 0.710, T_max = 0.750	l = −15→15
15193 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0393P)² + 3.5087P] where P = (F_o² + 2F_c²)/3
3449 reflections	(Δ/σ)_max = 0.001
286 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Cu(C₇H₅O₂)(C₁₂H₈N₂)₂]Cl·2C₇H₆O₂	V = 3922.1 (14) Å³
M_r = 824.74	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.724 (3) Å	µ = 0.68 mm⁻¹
b = 19.288 (4) Å	T = 293 K
c = 13.295 (3) Å	0.35 × 0.31 × 0.28 mm
β = 113.86 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3449 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2623 reflections with I > 2σ(I)
T_min = 0.710, T_max = 0.750	R_int = 0.029
15193 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.33 e Å⁻³
3449 reflections	Δρ_min = −0.45 e Å⁻³
286 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 > 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	Occ. (<1)
Cu	0.5000	0.26282 (3)	0.2500	0.05651 (17)
N1	0.40747 (13)	0.19982 (11)	0.12871 (18)	0.0554 (5)
N2	0.40438 (13)	0.26263 (12)	0.30525 (18)	0.0565 (5)
O1	0.4521 (4)	0.3849 (3)	0.1410 (5)	0.090 (2)	0.50
O2	0.5351 (3)	0.3568 (3)	0.3129 (5)	0.0600 (12)	0.50
C1	0.5000	0.4012 (3)	0.2500	0.0678 (11)
C2	0.5084 (4)	0.47718 (18)	0.2698 (3)	0.0556 (17)	0.50
C3	0.4829 (4)	0.5284 (3)	0.1894 (2)	0.0788 (19)	0.50
H3A	0.4598	0.5159	0.1131	0.095*	0.50
C4	0.4907 (5)	0.5979 (2)	0.2196 (3)	0.075 (3)	0.50
H4A	0.4731	0.6333	0.1641	0.090*	0.50
C5	0.5240 (5)	0.61615 (16)	0.3302 (4)	0.084 (3)	0.50
H5A	0.5295	0.6641	0.3511	0.100*	0.50
C6	0.5495 (3)	0.5649 (2)	0.4106 (3)	0.0794 (18)	0.50
H6A	0.5726	0.5775	0.4869	0.095*	0.50
C7	0.5417 (3)	0.49540 (19)	0.3803 (3)	0.0639 (15)	0.50
H7A	0.5593	0.4600	0.4358	0.077*	0.50
C8	0.4095 (2)	0.16743 (16)	0.0414 (2)	0.0694 (8)
H8A	0.4614	0.1678	0.0313	0.083*
C9	0.3373 (2)	0.13300 (16)	−0.0355 (3)	0.0791 (9)
H9A	0.3417	0.1106	−0.0950	0.095*
C10	0.2608 (2)	0.13242 (17)	−0.0231 (3)	0.0794 (9)
H10A	0.2123	0.1097	−0.0742	0.095*
C11	0.25483 (17)	0.16598 (14)	0.0667 (2)	0.0620 (7)
C12	0.17667 (18)	0.16982 (17)	0.0868 (3)	0.0790 (9)
H12A	0.1260	0.1485	0.0379	0.095*
C13	0.17515 (18)	0.20324 (17)	0.1738 (3)	0.0773 (9)
H13A	0.1231	0.2055	0.1835	0.093*
C14	0.25144 (16)	0.23560 (14)	0.2524 (2)	0.0596 (7)
C15	0.25428 (19)	0.27038 (17)	0.3459 (3)	0.0726 (8)
H15A	0.2041	0.2741	0.3596	0.087*
C16	0.3303 (2)	0.29866 (18)	0.4164 (3)	0.0773 (9)
H16A	0.3330	0.3211	0.4796	0.093*
C17	0.40467 (19)	0.29405 (17)	0.3938 (3)	0.0728 (8)
H17A	0.4565	0.3138	0.4430	0.087*
C18	0.32904 (15)	0.23281 (13)	0.2352 (2)	0.0502 (6)
C19	0.33051 (15)	0.19836 (13)	0.1411 (2)	0.0509 (6)
C20	0.6442 (2)	0.89663 (16)	0.5209 (3)	0.0723 (8)
C21	0.6652 (2)	0.94046 (15)	0.6202 (3)	0.0673 (8)
C22	0.7514 (2)	0.9571 (2)	0.6830 (3)	0.0868 (10)
H22A	0.7949	0.9405	0.6626	0.104*
C23	0.7738 (3)	0.9976 (2)	0.7744 (3)	0.1056 (12)
H23A	0.8322	1.0083	0.8157	0.127*
C24	0.7114 (3)	1.0223 (2)	0.8054 (4)	0.1033 (12)
H24A	0.7268	1.0498	0.8680	0.124*
C25	0.6259 (3)	1.0067 (2)	0.7445 (4)	0.1094 (14)
H25A	0.5833	1.0236	0.7662	0.131*
C26	0.6014 (2)	0.96621 (18)	0.6513 (3)	0.0901 (11)
H26A	0.5427	0.9564	0.6100	0.108*
Cl	0.5000	0.80270 (7)	0.2500	0.0916 (4)
O4	0.69924 (15)	0.87024 (14)	0.4972 (2)	0.1004 (8)
O3	0.55968 (17)	0.88975 (14)	0.4593 (2)	0.0977 (8)
H31	0.544 (3)	0.867 (2)	0.400 (3)	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0442 (3)	0.0686 (3)	0.0647 (3)	0.000	0.0303 (2)	0.000
N1	0.0514 (12)	0.0577 (13)	0.0631 (13)	0.0028 (10)	0.0293 (11)	−0.0023 (11)
N2	0.0457 (11)	0.0689 (14)	0.0605 (13)	−0.0025 (10)	0.0274 (11)	−0.0060 (11)
O1	0.074 (3)	0.099 (5)	0.066 (4)	0.006 (3)	−0.003 (3)	−0.021 (3)
O2	0.048 (3)	0.066 (3)	0.065 (3)	−0.003 (2)	0.021 (3)	−0.001 (2)
C1	0.043 (2)	0.069 (3)	0.090 (4)	0.000	0.025 (2)	0.000
C2	0.036 (3)	0.071 (3)	0.057 (5)	0.001 (4)	0.015 (4)	0.008 (3)
C3	0.051 (4)	0.108 (6)	0.068 (4)	0.009 (4)	0.014 (3)	0.018 (4)
C4	0.066 (5)	0.059 (4)	0.099 (10)	0.010 (5)	0.031 (7)	0.030 (4)
C5	0.066 (5)	0.062 (4)	0.118 (8)	0.009 (4)	0.033 (6)	−0.016 (5)
C6	0.086 (4)	0.067 (4)	0.077 (4)	0.000 (3)	0.025 (4)	−0.008 (4)
C7	0.065 (4)	0.060 (4)	0.062 (4)	0.000 (3)	0.020 (3)	−0.004 (3)
C8	0.0703 (18)	0.071 (2)	0.077 (2)	0.0054 (16)	0.0401 (17)	−0.0067 (16)
C9	0.088 (2)	0.071 (2)	0.075 (2)	−0.0002 (18)	0.0290 (18)	−0.0246 (17)
C10	0.0640 (19)	0.075 (2)	0.085 (2)	−0.0066 (16)	0.0146 (17)	−0.0168 (18)
C11	0.0550 (16)	0.0535 (16)	0.0726 (19)	−0.0011 (13)	0.0207 (14)	−0.0038 (14)
C12	0.0483 (16)	0.078 (2)	0.105 (3)	−0.0131 (15)	0.0248 (17)	−0.009 (2)
C13	0.0491 (16)	0.081 (2)	0.108 (3)	−0.0054 (15)	0.0388 (18)	0.000 (2)
C14	0.0462 (14)	0.0615 (17)	0.0778 (18)	0.0016 (13)	0.0322 (14)	0.0083 (15)
C15	0.0616 (18)	0.086 (2)	0.090 (2)	0.0066 (16)	0.0514 (18)	0.0042 (18)
C16	0.071 (2)	0.097 (2)	0.080 (2)	0.0014 (18)	0.0474 (18)	−0.0120 (18)
C17	0.0627 (17)	0.093 (2)	0.0726 (19)	−0.0080 (16)	0.0373 (16)	−0.0174 (17)
C18	0.0423 (13)	0.0502 (14)	0.0619 (15)	0.0033 (11)	0.0248 (12)	0.0061 (13)
C19	0.0450 (13)	0.0464 (15)	0.0629 (16)	0.0042 (11)	0.0237 (13)	0.0044 (12)
C20	0.080 (2)	0.0680 (19)	0.093 (2)	0.0097 (16)	0.061 (2)	0.0170 (17)
C21	0.083 (2)	0.0550 (17)	0.088 (2)	0.0119 (15)	0.0592 (19)	0.0123 (15)
C22	0.073 (2)	0.106 (3)	0.093 (3)	0.0252 (19)	0.044 (2)	0.014 (2)
C23	0.089 (3)	0.132 (4)	0.093 (3)	0.011 (2)	0.034 (2)	−0.005 (3)
C24	0.115 (3)	0.106 (3)	0.105 (3)	−0.002 (3)	0.061 (3)	−0.014 (2)
C25	0.115 (3)	0.105 (3)	0.146 (4)	−0.003 (3)	0.093 (3)	−0.031 (3)
C26	0.084 (2)	0.085 (2)	0.129 (3)	−0.0038 (18)	0.072 (2)	−0.016 (2)
Cl	0.0794 (8)	0.0839 (8)	0.1148 (10)	0.000	0.0425 (7)	0.000
O4	0.0964 (16)	0.121 (2)	0.1100 (18)	0.0257 (15)	0.0688 (15)	−0.0062 (15)
O3	0.0869 (17)	0.113 (2)	0.118 (2)	−0.0093 (14)	0.0673 (17)	−0.0255 (16)

Geometric parameters (Å, º) top

Cu—O2	1.984 (5)	C11—C19	1.399 (4)
Cu—O2ⁱ	1.984 (5)	C11—C12	1.438 (4)
Cu—N2ⁱ	2.012 (2)	C12—C13	1.334 (4)
Cu—N2	2.012 (2)	C12—H12A	0.9300
Cu—N1	2.110 (2)	C13—C14	1.425 (4)
Cu—N1ⁱ	2.110 (2)	C13—H13A	0.9300
N1—C8	1.330 (3)	C14—C15	1.396 (4)
N1—C19	1.362 (3)	C14—C18	1.407 (3)
N2—C17	1.322 (3)	C15—C16	1.352 (4)
N2—C18	1.355 (3)	C15—H15A	0.9300
O1—C1	1.378 (6)	C16—C17	1.395 (4)
O2—C1	1.174 (6)	C16—H16A	0.9300
C1—C2	1.486 (6)	C17—H17A	0.9300
C2—C3	1.3900	C18—C19	1.425 (3)
C2—C7	1.3900	C20—O4	1.200 (3)
C3—C4	1.3900	C20—O3	1.323 (4)
C3—H3A	0.9600	C20—C21	1.485 (4)
C4—C5	1.3900	C21—C22	1.380 (5)
C4—H4A	0.9600	C21—C26	1.384 (4)
C5—C6	1.3900	C22—C23	1.363 (5)
C5—H5A	0.9601	C22—H22A	0.9300
C6—C7	1.3900	C23—C24	1.355 (5)
C6—H6A	0.9599	C23—H23A	0.9300
C7—H7A	0.9601	C24—C25	1.361 (5)
C8—C9	1.395 (4)	C24—H24A	0.9300
C8—H8A	0.9300	C25—C26	1.379 (5)
C9—C10	1.356 (4)	C25—H25A	0.9300
C9—H9A	0.9300	C26—H26A	0.9300
C10—C11	1.395 (4)	Cl—Clⁱ	0.000 (3)
C10—H10A	0.9300	O3—H31	0.85 (4)

O2—Cu—O2ⁱ	47.8 (3)	C11—C10—H10A	120.1
O2—Cu—N2ⁱ	90.69 (16)	C10—C11—C19	117.1 (3)
O2ⁱ—Cu—N2ⁱ	89.49 (16)	C10—C11—C12	124.5 (3)
O2—Cu—N2	89.49 (16)	C19—C11—C12	118.4 (3)
O2ⁱ—Cu—N2	90.69 (16)	C13—C12—C11	121.6 (3)
N2ⁱ—Cu—N2	179.80 (13)	C13—C12—H12A	119.2
O2—Cu—N1	148.10 (18)	C11—C12—H12A	119.2
O2ⁱ—Cu—N1	101.76 (18)	C12—C13—C14	121.5 (3)
N2ⁱ—Cu—N1	99.53 (8)	C12—C13—H13A	119.3
N2—Cu—N1	80.35 (8)	C14—C13—H13A	119.3
O2—Cu—N1ⁱ	101.76 (18)	C15—C14—C18	117.5 (3)
O2ⁱ—Cu—N1ⁱ	148.10 (18)	C15—C14—C13	124.1 (3)
N2ⁱ—Cu—N1ⁱ	80.35 (8)	C18—C14—C13	118.4 (3)
N2—Cu—N1ⁱ	99.53 (8)	C16—C15—C14	119.7 (2)
N1—Cu—N1ⁱ	109.69 (12)	C16—C15—H15A	120.2
C8—N1—C19	117.0 (2)	C14—C15—H15A	120.2
C8—N1—Cu	131.86 (18)	C15—C16—C17	119.7 (3)
C19—N1—Cu	110.87 (16)	C15—C16—H16A	120.2
C17—N2—C18	118.3 (2)	C17—C16—H16A	120.2
C17—N2—Cu	127.38 (19)	N2—C17—C16	122.6 (3)
C18—N2—Cu	113.88 (16)	N2—C17—H17A	118.7
C1—O2—Cu	112.8 (4)	C16—C17—H17A	118.7
O2—C1—O1	119.6 (6)	N2—C18—C14	122.3 (2)
O2—C1—C2	127.5 (4)	N2—C18—C19	117.4 (2)
O1—C1—C2	112.6 (4)	C14—C18—C19	120.3 (2)
C3—C2—C7	120.0	N1—C19—C11	123.5 (2)
C3—C2—C1	126.0 (3)	N1—C19—C18	116.7 (2)
C7—C2—C1	113.9 (3)	C11—C19—C18	119.8 (2)
C4—C3—C2	120.0	O4—C20—O3	122.4 (3)
C4—C3—H3A	120.0	O4—C20—C21	122.9 (3)
C2—C3—H3A	120.0	O3—C20—C21	114.6 (3)
C3—C4—C5	120.0	C22—C21—C26	118.6 (3)
C3—C4—H4A	120.0	C22—C21—C20	119.0 (3)
C5—C4—H4A	120.0	C26—C21—C20	122.5 (3)
C4—C5—C6	120.0	C23—C22—C21	121.1 (3)
C4—C5—H5A	120.0	C23—C22—H22A	119.5
C6—C5—H5A	120.0	C21—C22—H22A	119.5
C7—C6—C5	120.0	C24—C23—C22	120.3 (4)
C7—C6—H6A	120.0	C24—C23—H23A	119.8
C5—C6—H6A	120.0	C22—C23—H23A	119.8
C6—C7—C2	120.0	C23—C24—C25	119.6 (4)
C6—C7—H7A	120.0	C23—C24—H24A	120.2
C2—C7—H7A	120.0	C25—C24—H24A	120.2
N1—C8—C9	122.9 (3)	C24—C25—C26	121.3 (3)
N1—C8—H8A	118.5	C24—C25—H25A	119.4
C9—C8—H8A	118.5	C26—C25—H25A	119.4
C10—C9—C8	119.6 (3)	C25—C26—C21	119.2 (4)
C10—C9—H9A	120.2	C25—C26—H26A	120.4
C8—C9—H9A	120.2	C21—C26—H26A	120.4
C9—C10—C11	119.9 (3)	C20—O3—H31	119 (3)
C9—C10—H10A	120.1

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···Cl	0.96	2.94	3.728 (4)	140
O3—H31···Cl	0.85 (4)	2.20 (4)	3.051 (3)	177 (4)
O3—H31···Clⁱ	0.85 (4)	2.20 (4)	3.051 (3)	177 (4)
C24—H24A···O4ⁱⁱ	0.93	2.49	3.355 (5)	155
C8—H8A···O3ⁱⁱⁱ	0.93	2.47	3.307 (4)	149
C10—H10A···O1^iv	0.93	2.53	3.275 (7)	138
C12—H12A···O1^iv	0.93	2.30	3.106 (7)	146

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

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₅O₂)(C₁₂H₈N₂)₂]Cl·2C₇H₆O₂
M_r	824.74
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	16.724 (3), 19.288 (4), 13.295 (3)
β (°)	113.86 (3)
V (Å³)	3922.1 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.68
Crystal size (mm)	0.35 × 0.31 × 0.28

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.710, 0.750
No. of measured, independent and observed [I > 2σ(I)] reflections	15193, 3449, 2623
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.101, 1.08
No. of reflections	3449
No. of parameters	286
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.45

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···Cl	0.96	2.94	3.728 (4)	139.9
O3—H31···Cl	0.85 (4)	2.20 (4)	3.051 (3)	177 (4)
O3—H31···Clⁱ	0.85 (4)	2.20 (4)	3.051 (3)	177 (4)
C24—H24A···O4ⁱⁱ	0.93	2.49	3.355 (5)	155.3
C8—H8A···O3ⁱⁱⁱ	0.93	2.47	3.307 (4)	149.0
C10—H10A···O1^iv	0.93	2.53	3.275 (7)	137.7
C12—H12A···O1^iv	0.93	2.30	3.106 (7)	145.5

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

Acknowledgements

This project was supported by the National Natural Science Foundation of China (grant No. 20072022), the Science and Technology Department of Zhejiang Province (grant No. 2006 C21105) and the Education Department of Zhejiang Province. Sincere thanks are also extended to the K. C. Wong Magna Fund of Ningbo University.

References

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