(2,2′-Bipyridine)(2-{1-[2-(dimethyl­amino)ethyl­imino]eth­yl}-4-methoxy­phenolato)copper(II) perchlorate

Tsai, Y.-H.; Hung, W.-C.; Lin, C.-C.

doi:10.1107/S1600536809014573

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page m578

doi:10.1107/S1600536809014573

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(2,2′-Bipyridine)(2-{1-[2-(dimethylamino)ethylimino]ethyl}-4-methoxyphenolato)copper(II) perchlorate

Yueh-Hsuan Tsai,^a Wen-Chou Hung ^a and Chu-Chieh Lin ^a ^*

^aDepartment of Chemistry, National Chung Hsing University, Taichung 402, Taiwan, Republic of China
^*Correspondence e-mail: cchlin@mail.nchu.edu.tw

(Received 24 March 2009; accepted 20 April 2009; online 30 April 2009)

The Cu atom of the title complex, [Cu(C₁₃H₁₉N₂O₂)(C₁₀H₈N₂)]ClO₄, has a distorted square-pyramidal geometry with all three of the donor atoms from the N,N′,O-tridentate Schiff base ligand in the equatorial positions and the bipyridine N atoms in an equatorial–axial binding mode. The Cu atom is 0.1801 (11) Å above the N₃O mean basal plane.

Related literature

For the development of efficient catalytic systems for the coupling of CO₂ with heterocycles into polycarbonates, see: Inoue et al. (1969 ). For the synthesis and catalytic studies of a series of bis–(salicylaldiminato)zinc complexes, see: Darensbourg et al. (2001 ). For similar complexes, see: Dhar et al. (2006 ); Shen et al. (2003 ). For the synthesis, see: Hung & Lin (2009 ); Hung et al. (2008 ); For the chemical activity of complexes, see: Noh et al. (2007 ).

Experimental

Crystal data

[Cu(C₁₃H₁₉N₂O₂)(C₁₀H₈N₂)]ClO₄
M_r = 554.49
Monoclinic, P 2₁ /c
a = 10.1588 (10) Å
b = 18.2163 (17) Å
c = 13.3764 (13) Å
β = 92.610 (2)°
V = 2472.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 293 K
0.34 × 0.26 × 0.15 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.719, T_max = 0.860
13946 measured reflections
4859 independent reflections
3488 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.105
S = 0.98
4859 reflections
319 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014573/rk2135sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809014573/rk2135Isup2.hkl

checkCIF report

Comment top

Though many bacteria convert CO₂ into organic compounds by photosynthesis, utilization of CO₂ as a chemical feedstock in industrial and laboratory is rare. Recently, reuse of CO₂ has received great attention because of environmental concern. Polycarbonates (PC) have been wildly used in the modern chemical industry. Co–polymerization of CO₂ with olefins may benefit from reducing the release of CO₂ and generating potential industrial useful PCs. Therefore, there has been increasing interest in the development of efficient catalytic systems for the coupling of CO₂ with heterocycles into polycarbonates (Inoue et al., 1969). One of the major successes is the utilization of epoxides and CO₂ as starting materials to prepare PCs and/or cyclic carbonates in the presence of a transition metal catalyst. Recently, Darensbourg et al., (2001) disclosed the synthesis, characterization and catalytic studies of a series of bis–(salicylaldiminato)zinc complexes, in which the most active catalyst for co–polymerization of cyclohexene oxide and CO₂ giving poly(cyclohexene carbonate) (>99% carbonate linkages, Mn = 41000 g^.mol^-1, Mw/Mn = 10.3) with a turnover frequency of 6.9 h^-1. In addition, Shen et al. (2003) reported that binaphthyldiaminosalen–type Zn, Cu, and Co complexes efficiently catalyzed reactions of epoxides with CO₂ to achieve five–membered ring cyclic carbonates in the presence of various catalytic amounts of organic bases. Noh et al., (2007) disclosed catalytic studies of the binary system of [(salen)Co(III)complex] / (quaternary ammonium salt) for co–polymerization of propylene oxide and CO₂. Most recently, a series of N,N,O–tridentate Schiff base zinc– and magnesium–complexes have been reported to be effective initiators / catalyst for ROP of lactide (Hung et al., 2008; Hung & Lin, 2009). We report herein the synthesis and crystal structure of [LCu(bipy)]ClO₄, where L is title tridentate ligand and bipy is 2,2'–bipyridine, a potential catalyst for CO₂ / epoxide coupling co–polymerization.

The solid structure of [LCu(bipy)]⁺ ion reveals a monomeric Cu^II complex containing a six–member and a five–member ring coordinated from the tridentate salicylideneiminate ligand and a five–member ring coordinated from the bipyridine ligand. The geometry around Cu atom is penta–coordinated with a slight distorted square pyramidal environment in which all three of the N,N,O–tridentate donor atoms and one of the N atoms of the bipyridine lignad sitting on the equatorial plane, and another N atom of the bipyridine ligand at the axial position. The distances between the Cu atom and O1, N1, N2, N3 and N4 are 1.903 (2), 1.964 (2), 2.076 (2), 2.208 (2) and 2.044 (2) Å, respectively which are all within a normal distance for a Cu—O and Cu—N distance. These bond distances are similar to those found in other Schiff base Cu^II complexes (Dhar et al., 2006).

Related literature top

For the development of efficient catalytic systems for the coupling of CO₂ with heterocycles into polycarbonates, see: Inoue et al. (1969). For the synthesis and catalytic studies of a series of bis–(salicylaldiminato)zinc complexes, see: Darensbourg et al. (2001). For similar complexes, see: Dhar et al. (2006); Shen et al. (2003). For the synthesis, see: Hung & Lin (2009); Hung et al. (2008); For the chemical activity of complexes, see: Noh et al. (2007).

Experimental top

The ligand, 2–{1–[2–(dimethylamino)ethylimino]ethyl}–4–methoxyphenol was prepared according to the method reported previously (Hung et al., 2008). The title complex was synthesized by the following procedures: Cu(OAc)₂^.H₂O (0.197 g, 1.00 mmol) and 2,2'–bipyridine (0.199 g, 1.28 mmol) was stirred in EtOH (15 ml) at room temperature for 0.5 h. The 2–{1–[2–(dimethylamino)ethylimino]ethyl}–4–methoxyphenol (0.298 g, 1.0 mmol) in EtOH (10 ml) was added. The reaction mixture was then stirred for another 1 h, and an 10 ml ethanolic solution of NaClO₄ (0.122 g, 1.0 mmol) was added producing green precipitate. The product was isolated by filtration and the resulting precipitate was crystallized from EtOH to yield green crystals.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecular structure with the atom numbering scheme. The displacement ellipsoids are shown at the 20% probability level. H atoms are presented as a small spheres of arbitrary radius.

(2,2'-Bipyridine)(2-{1-[2-(dimethylamino)ethylimino]ethyl}-4- methoxyphenolato)copper(II) perchlorate top

Crystal data top

[Cu(C₁₃H₁₉N₂O₂)(C₁₀H₈N₂)]ClO₄	F(000) = 1148
M_r = 554.49	D_x = 1.489 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4710 reflections
a = 10.1588 (10) Å	θ = 2.3–25.6°
b = 18.2163 (17) Å	µ = 1.04 mm⁻¹
c = 13.3764 (13) Å	T = 293 K
β = 92.610 (2)°	Parallelpiped, green
V = 2472.8 (4) Å³	0.34 × 0.26 × 0.15 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	4859 independent reflections
Radiation source: fine–focus sealed tube	3488 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.719, T_max = 0.860	k = −22→16
13946 measured reflections	l = −16→15

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) = 0.105	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.06P)²] where P = (F_o² + 2F_c²)/3
4859 reflections	(Δ/σ)_max = 0.001
319 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Cu(C₁₃H₁₉N₂O₂)(C₁₀H₈N₂)]ClO₄	V = 2472.8 (4) Å³
M_r = 554.49	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.1588 (10) Å	µ = 1.04 mm⁻¹
b = 18.2163 (17) Å	T = 293 K
c = 13.3764 (13) Å	0.34 × 0.26 × 0.15 mm
β = 92.610 (2)°

Data collection top

Bruker SMART 1000 CCD diffractometer	4859 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3488 reflections with I > 2σ(I)
T_min = 0.719, T_max = 0.860	R_int = 0.037
13946 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 0.98	Δρ_max = 0.33 e Å⁻³
4859 reflections	Δρ_min = −0.30 e Å⁻³
319 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
Cu	0.62390 (3)	0.172001 (16)	0.82971 (2)	0.04095 (12)
O1	0.6832 (2)	0.15346 (10)	0.96441 (14)	0.0532 (5)
O2	0.9049 (3)	−0.10697 (14)	1.0997 (2)	0.1017 (10)
N1	0.5494 (2)	0.07290 (12)	0.81586 (16)	0.0457 (5)
N2	0.4979 (2)	0.19843 (13)	0.70841 (18)	0.0528 (6)
N3	0.8094 (2)	0.16361 (12)	0.75071 (17)	0.0469 (6)
N4	0.6989 (2)	0.27569 (11)	0.84447 (15)	0.0412 (5)
C1	0.7293 (3)	0.08881 (15)	0.9916 (2)	0.0455 (6)
C2	0.8227 (3)	0.08568 (17)	1.0724 (2)	0.0583 (8)
H2A	0.8483	0.1293	1.1039	0.070*
C3	0.8779 (4)	0.02114 (19)	1.1069 (2)	0.0681 (9)
H3A	0.9395	0.0215	1.1605	0.082*
C4	0.8411 (4)	−0.04469 (18)	1.0612 (2)	0.0665 (9)
C5	0.7497 (3)	−0.04455 (16)	0.9842 (2)	0.0576 (8)
H5A	0.7257	−0.0890	0.9544	0.069*
C6	0.6895 (3)	0.02080 (15)	0.94751 (19)	0.0439 (6)
C7	0.5849 (3)	0.01591 (15)	0.8687 (2)	0.0447 (7)
C8	0.5192 (3)	−0.05759 (16)	0.8497 (2)	0.0605 (8)
H8A	0.5193	−0.0850	0.9111	0.079 (10)*
H8B	0.5666	−0.0844	0.8011	0.102 (13)*
H8C	0.4300	−0.0500	0.8250	0.098 (13)*
C9	0.4456 (3)	0.06785 (18)	0.7363 (2)	0.0629 (8)
H9A	0.3599	0.0752	0.7639	0.075*
H9B	0.4469	0.0197	0.7054	0.075*
C10	0.4709 (3)	0.12658 (16)	0.6597 (2)	0.0603 (8)
H10A	0.5457	0.1125	0.6214	0.072*
H10B	0.3947	0.1309	0.6137	0.072*
C11	0.3779 (4)	0.2319 (2)	0.7440 (3)	0.0901 (13)
H11A	0.3197	0.2441	0.6879	0.135*
H11B	0.4002	0.2758	0.7809	0.135*
H11C	0.3349	0.1980	0.7867	0.135*
C12	0.5537 (4)	0.24885 (18)	0.6336 (2)	0.0728 (10)
H12A	0.4889	0.2579	0.5805	0.109*
H12B	0.6301	0.2267	0.6066	0.109*
H12C	0.5781	0.2944	0.6654	0.109*
C13	0.8909 (5)	−0.1720 (2)	1.0445 (3)	0.1034 (15)
H13A	0.9394	−0.2106	1.0783	0.155*
H13B	0.9244	−0.1648	0.9792	0.155*
H13C	0.7994	−0.1852	1.0380	0.155*
C14	0.8536 (3)	0.10711 (16)	0.6971 (2)	0.0578 (8)
H14A	0.8076	0.0630	0.6976	0.069*
C15	0.9634 (3)	0.11167 (19)	0.6418 (2)	0.0630 (9)
H15A	0.9903	0.0718	0.6045	0.076*
C16	1.0329 (3)	0.1763 (2)	0.6427 (3)	0.0689 (9)
H16A	1.1076	0.1809	0.6055	0.083*
C17	0.9908 (3)	0.23447 (17)	0.6995 (2)	0.0572 (8)
H17A	1.0379	0.2783	0.7021	0.069*
C18	0.8784 (3)	0.22671 (14)	0.75206 (19)	0.0415 (6)
C19	0.8210 (3)	0.28739 (14)	0.81221 (18)	0.0402 (6)
C20	0.8879 (3)	0.35225 (16)	0.8336 (2)	0.0531 (7)
H20A	0.9728	0.3592	0.8123	0.064*
C21	0.8265 (3)	0.40656 (17)	0.8872 (2)	0.0611 (8)
H21A	0.8702	0.4503	0.9025	0.073*
C22	0.7019 (3)	0.39554 (15)	0.9173 (2)	0.0546 (8)
H22A	0.6587	0.4319	0.9520	0.066*
C23	0.6409 (3)	0.32963 (14)	0.8954 (2)	0.0480 (7)
H23A	0.5561	0.3220	0.9166	0.058*
Cl	0.25347 (7)	0.09143 (4)	0.40216 (5)	0.05096 (19)
O3	0.2755 (3)	0.16261 (12)	0.4419 (2)	0.0957 (9)
O4	0.2085 (3)	0.09639 (16)	0.30025 (18)	0.0956 (9)
O5	0.1576 (3)	0.05517 (15)	0.4574 (2)	0.0958 (8)
O6	0.3729 (2)	0.05090 (16)	0.4085 (2)	0.0970 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0450 (2)	0.03477 (19)	0.04338 (19)	−0.00436 (14)	0.00530 (14)	−0.00633 (13)
O1	0.0719 (14)	0.0383 (11)	0.0488 (11)	−0.0068 (9)	−0.0037 (10)	−0.0082 (8)
O2	0.157 (3)	0.0660 (17)	0.0788 (17)	0.0307 (17)	−0.0360 (18)	0.0011 (13)
N1	0.0480 (14)	0.0429 (13)	0.0461 (12)	−0.0095 (11)	0.0028 (10)	−0.0070 (11)
N2	0.0570 (15)	0.0454 (14)	0.0554 (14)	0.0058 (12)	−0.0036 (12)	−0.0100 (11)
N3	0.0431 (13)	0.0430 (14)	0.0552 (14)	0.0014 (10)	0.0088 (11)	−0.0067 (10)
N4	0.0466 (13)	0.0356 (12)	0.0416 (12)	−0.0007 (10)	0.0033 (10)	−0.0018 (9)
C1	0.0533 (17)	0.0415 (16)	0.0424 (14)	−0.0072 (13)	0.0103 (12)	−0.0023 (12)
C2	0.071 (2)	0.0517 (19)	0.0519 (17)	−0.0082 (16)	−0.0031 (15)	−0.0078 (14)
C3	0.082 (2)	0.070 (2)	0.0515 (18)	−0.0007 (19)	−0.0059 (17)	−0.0052 (16)
C4	0.089 (3)	0.057 (2)	0.0532 (18)	0.0107 (18)	0.0023 (18)	−0.0003 (15)
C5	0.080 (2)	0.0413 (17)	0.0515 (17)	−0.0015 (15)	0.0065 (16)	−0.0040 (13)
C6	0.0526 (16)	0.0415 (15)	0.0383 (14)	−0.0049 (13)	0.0089 (12)	−0.0015 (11)
C7	0.0517 (16)	0.0389 (15)	0.0451 (15)	−0.0108 (13)	0.0191 (13)	−0.0092 (12)
C8	0.074 (2)	0.0480 (18)	0.0608 (19)	−0.0214 (16)	0.0146 (17)	−0.0062 (15)
C9	0.061 (2)	0.060 (2)	0.066 (2)	−0.0155 (16)	−0.0089 (16)	−0.0077 (16)
C10	0.070 (2)	0.0530 (19)	0.0569 (18)	0.0031 (16)	−0.0116 (16)	−0.0116 (14)
C11	0.063 (2)	0.103 (3)	0.103 (3)	0.028 (2)	−0.010 (2)	−0.035 (2)
C12	0.099 (3)	0.055 (2)	0.063 (2)	0.0052 (19)	−0.0126 (19)	0.0072 (16)
C13	0.149 (4)	0.068 (3)	0.092 (3)	0.037 (3)	−0.011 (3)	0.005 (2)
C14	0.0549 (18)	0.0486 (18)	0.070 (2)	0.0049 (14)	0.0082 (15)	−0.0145 (15)
C15	0.060 (2)	0.066 (2)	0.063 (2)	0.0147 (17)	0.0092 (16)	−0.0190 (16)
C16	0.0503 (19)	0.091 (3)	0.067 (2)	0.0089 (18)	0.0195 (16)	−0.0087 (18)
C17	0.0470 (17)	0.059 (2)	0.0658 (19)	−0.0041 (14)	0.0093 (15)	0.0006 (15)
C18	0.0399 (14)	0.0445 (15)	0.0398 (14)	0.0019 (12)	−0.0011 (11)	0.0024 (11)
C19	0.0429 (15)	0.0402 (15)	0.0371 (13)	−0.0018 (12)	−0.0026 (11)	0.0038 (11)
C20	0.0515 (18)	0.0513 (18)	0.0566 (17)	−0.0134 (14)	0.0023 (14)	−0.0014 (14)
C21	0.076 (2)	0.0430 (17)	0.0639 (19)	−0.0151 (16)	−0.0035 (17)	−0.0052 (14)
C22	0.077 (2)	0.0381 (16)	0.0488 (17)	0.0009 (15)	0.0025 (15)	−0.0054 (12)
C23	0.0541 (17)	0.0423 (16)	0.0480 (16)	0.0021 (13)	0.0060 (13)	−0.0046 (12)
Cl	0.0475 (4)	0.0508 (4)	0.0552 (4)	0.0010 (3)	0.0103 (3)	0.0000 (3)
O3	0.138 (3)	0.0527 (15)	0.097 (2)	−0.0073 (15)	0.0050 (18)	−0.0065 (13)
O4	0.0810 (17)	0.146 (3)	0.0593 (15)	0.0118 (17)	−0.0038 (13)	−0.0072 (15)
O5	0.0868 (18)	0.0864 (19)	0.118 (2)	−0.0077 (15)	0.0486 (16)	0.0223 (15)
O6	0.0599 (15)	0.113 (2)	0.118 (2)	0.0323 (15)	0.0115 (14)	0.0019 (17)

Geometric parameters (Å, º) top

Cu—O1	1.9037 (19)	C9—H9B	0.9700
Cu—N1	1.963 (2)	C10—H10A	0.9700
Cu—N4	2.043 (2)	C10—H10B	0.9700
Cu—N2	2.077 (2)	C11—H11A	0.9600
Cu—N3	2.207 (2)	C11—H11B	0.9600
O1—C1	1.313 (3)	C11—H11C	0.9600
O2—C4	1.393 (4)	C12—H12A	0.9600
O2—C13	1.400 (4)	C12—H12B	0.9600
N1—C7	1.298 (3)	C12—H12C	0.9600
N1—C9	1.466 (3)	C13—H13A	0.9600
N2—C11	1.462 (4)	C13—H13B	0.9600
N2—C10	1.482 (4)	C13—H13C	0.9600
N2—C12	1.490 (4)	C14—C15	1.369 (4)
N3—C14	1.343 (3)	C14—H14A	0.9300
N3—C18	1.346 (3)	C15—C16	1.372 (4)
N4—C19	1.348 (3)	C15—H15A	0.9300
N4—C23	1.347 (3)	C16—C17	1.383 (4)
C1—C2	1.407 (4)	C16—H16A	0.9300
C1—C6	1.423 (4)	C17—C18	1.375 (4)
C2—C3	1.373 (4)	C17—H17A	0.9300
C2—H2A	0.9300	C18—C19	1.501 (4)
C3—C4	1.389 (4)	C19—C20	1.386 (4)
C3—H3A	0.9300	C20—C21	1.387 (4)
C4—C5	1.355 (4)	C20—H20A	0.9300
C5—C6	1.416 (4)	C21—C22	1.360 (4)
C5—H5A	0.9300	C21—H21A	0.9300
C6—C7	1.465 (4)	C22—C23	1.376 (4)
C7—C8	1.512 (4)	C22—H22A	0.9300
C8—H8A	0.9600	C23—H23A	0.9300
C8—H8B	0.9600	Cl—O5	1.413 (2)
C8—H8C	0.9600	Cl—O3	1.416 (2)
C9—C10	1.512 (4)	Cl—O6	1.419 (2)
C9—H9A	0.9700	Cl—O4	1.421 (2)

O1—Cu—N1	91.73 (9)	N2—C10—C9	111.1 (3)
O1—Cu—N4	88.40 (8)	N2—C10—H10A	109.4
N1—Cu—N4	179.21 (9)	C9—C10—H10A	109.4
O1—Cu—N2	159.65 (9)	N2—C10—H10B	109.4
N1—Cu—N2	85.30 (9)	C9—C10—H10B	109.4
N4—Cu—N2	94.31 (9)	H10A—C10—H10B	108.0
O1—Cu—N3	101.58 (9)	N2—C11—H11A	109.5
N1—Cu—N3	103.01 (9)	N2—C11—H11B	109.5
N4—Cu—N3	77.72 (8)	H11A—C11—H11B	109.5
N2—Cu—N3	98.71 (9)	N2—C11—H11C	109.5
C1—O1—Cu	121.01 (16)	H11A—C11—H11C	109.5
C4—O2—C13	117.4 (3)	H11B—C11—H11C	109.5
C7—N1—C9	121.2 (2)	N2—C12—H12A	109.5
C7—N1—Cu	125.99 (18)	N2—C12—H12B	109.5
C9—N1—Cu	112.81 (18)	H12A—C12—H12B	109.5
C11—N2—C10	111.8 (3)	N2—C12—H12C	109.5
C11—N2—C12	108.1 (3)	H12A—C12—H12C	109.5
C10—N2—C12	108.5 (2)	H12B—C12—H12C	109.5
C11—N2—Cu	109.6 (2)	O2—C13—H13A	109.5
C10—N2—Cu	103.51 (18)	O2—C13—H13B	109.5
C12—N2—Cu	115.31 (19)	H13A—C13—H13B	109.5
C14—N3—C18	118.4 (2)	O2—C13—H13C	109.5
C14—N3—Cu	128.5 (2)	H13A—C13—H13C	109.5
C18—N3—Cu	112.95 (17)	H13B—C13—H13C	109.5
C19—N4—C23	118.5 (2)	N3—C14—C15	122.8 (3)
C19—N4—Cu	117.37 (17)	N3—C14—H14A	118.6
C23—N4—Cu	123.61 (19)	C15—C14—H14A	118.6
O1—C1—C2	118.0 (2)	C14—C15—C16	118.6 (3)
O1—C1—C6	125.1 (3)	C14—C15—H15A	120.7
C2—C1—C6	116.9 (3)	C16—C15—H15A	120.7
C3—C2—C1	122.9 (3)	C15—C16—C17	119.3 (3)
C3—C2—H2A	118.5	C15—C16—H16A	120.3
C1—C2—H2A	118.5	C17—C16—H16A	120.3
C2—C3—C4	119.6 (3)	C18—C17—C16	119.1 (3)
C2—C3—H3A	120.2	C18—C17—H17A	120.4
C4—C3—H3A	120.2	C16—C17—H17A	120.4
C5—C4—C3	119.6 (3)	N3—C18—C17	121.7 (2)
C5—C4—O2	125.0 (3)	N3—C18—C19	114.9 (2)
C3—C4—O2	115.4 (3)	C17—C18—C19	123.4 (3)
C4—C5—C6	122.4 (3)	N4—C19—C20	121.2 (2)
C4—C5—H5A	118.8	N4—C19—C18	116.2 (2)
C6—C5—H5A	118.8	C20—C19—C18	122.6 (2)
C5—C6—C1	118.5 (3)	C21—C20—C19	119.1 (3)
C5—C6—C7	119.1 (2)	C21—C20—H20A	120.4
C1—C6—C7	122.3 (2)	C19—C20—H20A	120.4
N1—C7—C6	121.2 (2)	C22—C21—C20	119.6 (3)
N1—C7—C8	120.5 (3)	C22—C21—H21A	120.2
C6—C7—C8	118.3 (3)	C20—C21—H21A	120.2
C7—C8—H8A	109.5	C21—C22—C23	118.8 (3)
C7—C8—H8B	109.5	C21—C22—H22A	120.6
H8A—C8—H8B	109.5	C23—C22—H22A	120.6
C7—C8—H8C	109.5	N4—C23—C22	122.8 (3)
H8A—C8—H8C	109.5	N4—C23—H23A	118.6
H8B—C8—H8C	109.5	C22—C23—H23A	118.6
N1—C9—C10	108.0 (2)	O5—Cl—O3	109.42 (18)
N1—C9—H9A	110.1	O5—Cl—O6	109.47 (17)
C10—C9—H9A	110.1	O3—Cl—O6	109.50 (18)
N1—C9—H9B	110.1	O5—Cl—O4	109.41 (17)
C10—C9—H9B	110.1	O3—Cl—O4	109.93 (18)
H9A—C9—H9B	108.4	O6—Cl—O4	109.10 (17)

Experimental details

Crystal data
Chemical formula	[Cu(C₁₃H₁₉N₂O₂)(C₁₀H₈N₂)]ClO₄
M_r	554.49
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.1588 (10), 18.2163 (17), 13.3764 (13)
β (°)	92.610 (2)
V (Å³)	2472.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.34 × 0.26 × 0.15

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.719, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	13946, 4859, 3488
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.105, 0.98
No. of reflections	4859
No. of parameters	319
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.30

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

Financial support from the National Science Council of the Republic of China is gratefully appreciated. Helpful comments from the reviewers are also greatly appreciated.

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