Tetra-μ-benzoato-bis­[(6-methyl­quino­line)­copper(II)]

Yu, S.M.; Park, C.-H.; Kim, P.-G.; Kim, C.; Kim, Y.

doi:10.1107/S1600536808016516

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Pages m881-m882

doi:10.1107/S1600536808016516

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Tetra-μ-benzoato-bis[(6-methylquinoline)copper(II)]

Seung Man Yu,^a Chi-Ho Park,^b Pan-Gi Kim,^c Cheal Kim ^a ^* and Youngmee Kim ^d ^*

^aDepartment of Fine Chemistry, and Eco-Product and Materials Education Center, Seoul National University of Technology, Seoul 139-743, Republic of Korea, ^bNational Institute of Animal Science (NIAS), RDA, Suwon 441-350, Republic of Korea, ^cDepartment of Forest and Environment Resources, Kyungpook National University, Sangju 742-711, Republic of Korea, and ^dDepartment of Chemistry and Nano Sciences, Ewha Womans University, Seoul 120-750, Republic of Korea
^*Correspondence e-mail: chealkim@sunt.ac.kr, ymeekim@ewha.ac.kr

(Received 15 May 2008; accepted 30 May 2008; online 7 June 2008)

In the title compound, [Cu₂(C₇H₅O₂)₄(C₁₀H₉N)₂], the paddle-wheel-type dinuclear complex is constructed by four bridging benzoate groups and two terminal 6-methylquinoline ligands. The asymmetric unit contains one-half of the whole molecule, and there is an inversion center at the mid-point of the Cu⋯Cu bond. The octahedral coordination of each Cu atom, with four O atoms in the equatorial plane, is completed by the N atom of the 6-methylquinoline molecule [Cu—N = 2.212 (2) Å] and by another Cu atom [Cu⋯Cu = 2.6939 (13) Å]. The Cu atom lies 0.234 Å out of the plane of the four O atoms. The molecular packing is stabilized by one intramolecular C—H⋯O as well as C—H⋯π and π–π interactions.

Related literature

For related literature, see: Batten & Robson (1998 ); Chun et al. (2005 ); Cotton & Walton (1993 ); Janiak (2003 ); Lee et al. (2008 ); Mines et al. (2002 ); Pichon et al. (2007 ); Yoo et al. (2003 ).

Experimental

Crystal data

[Cu₂(C₇H₅O₂)₄(C₁₀H₉N)₂]
M_r = 897.88
Triclinic, $[P \overline 1]$
a = 10.420 (7) Å
b = 10.590 (7) Å
c = 10.751 (6) Å
α = 70.399 (11)°
β = 64.234 (10)°
γ = 81.107 (10)°
V = 1006.5 (11) Å³
Z = 1
Mo Kα radiation
μ = 1.12 mm⁻¹
T = 288 (2) K
0.10 × 0.08 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS: Bruker, 1997 ) T_min = 0.898, T_max = 0.915
5579 measured reflections
3848 independent reflections
3001 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.100
S = 1.04
3848 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C22–C27 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O11	0.93	2.50	3.047 (4)	118
C2—H2⋯Cg1ⁱ	0.93	2.82	3.734 (3)	168
Symmetry code: (i) x, y, z+1.

Table 2
π–π interactions (Å, °)

Cg2 is the centroid of ring C22–C27. The offset is defined as the distance between CgI and the perpendicular projection of CgJ on ring I.

CgI	CgJ	CgI⋯CgJ	Dihedral angle	Interplanar distance	Offset
Cg2	Cg2i	3.967 (4)	0	3.39	2.06
Symmetry code: (i) -x+2,-y+2,-z.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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 I, New_Global_Publ_Block. DOI: 10.1107/S1600536808016516/bx2146sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016516/bx2146Isup2.hkl

checkCIF report

Comment top

Coordination polymers comprised of metal ions and bridging ligands represent one of the most active areas of material science and chemical research due to their potential applications as functional materials ranging from catalysis, gas absorption, molecular recognition, optics, and so on (Batten & Robson, 1998; Chun et al., 2005; Mines et al., 2002; Janiak, 2003; Yoo et al., 2003). The continuing interest in this area is also due to their intriguing variety of architectures and topologies through the variation of building blocks and reaction conditions. The dinuclear metal carboxylates, M₂(O₂CR)₄, are one of the important building blocks for the study of structures of coordination polymers (Cotton & Walton, 1993) and copper(II) carboxylates among them are often used as building blocks to form a pillard-grid MOF with large pores (Pichon et al., 2007). We have also used copper(II) benzoate as a building block and reported the structure of copper(II) benzoate with quinoxaline (Lee, et al., 2008). In this work, we have employed 6-methylquinoline to investigate the substituent effect of an organic ligand on the structure of copper-benzoate containing coordination complexes.We report here on the structure of new copper(II) benzoate with 6-methylquinoline.

Asymmetric unit contains half of whole molecule, and there is an inversion center in the middle of Cu—Cu bond. Symmetric operation (-x + 1,-y + 2,-z + 1) produces a paddle-wheel type dinuclear copper-benzoate complex (Fig. 1). The paddle-wheel type dinuclear complex is constructed by four bridging benzoate groups and two terminal 6-methylquinoline ligands. The octahedral coordination of each Cu atom, with four oxygen atoms in the equatorial plane, is completed by nitrogen atom of 6-methylquinoline molecule (Cu—N 2.212 (2) Å) and by another copper atom (Cu···Cu 2.6939 (13) Å). The copper atom is 0.234 Å out of the plane of the four oxygen atoms.In the crystal structure the molecular packing is stabilized by one intramolecular C—H···O as well as C—H···π and π ···π interactions, Table, 1 and 2.

Related literature top

For related literature, see: Batten & Robson (1998); Chun et al. (2005); Cotton & Walton (1993); Janiak (2003); Lee et al. (2008); Mines et al. (2002); Pichon et al. (2007); Yoo et al. (2003).

Experimental top

19.0 mg (0.1 mmol) of Cu(NO₃)₂^.2.5H₂O and 28.0 mg (0.2 mmol) of C₆H₅COONH₄ were dissolved in 4 ml me thanol and carefully layered by 4 ml acetone solution of 6-methylquinoline ligand (29.0 mg, 0.2 mmol). Suitable crystals of the title compound for X-ray analysis were obtained in a few weeks.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. The structure of the title compound showing the atom-labeling scheme. Displacement ellipsoids are shown at the 30% probability level.

Tetra-µ-benzoato-bis[(6-methylquinoline)copper(II)] top

Crystal data top

[Cu₂(C₇H₅O₂)₄(C₁₀H₉N)₂]	Z = 1
M_r = 897.88	F(000) = 462
Triclinic, P1	D_x = 1.481 Mg m⁻³
a = 10.420 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.590 (7) Å	Cell parameters from 1441 reflections
c = 10.751 (6) Å	θ = 2.4–19.8°
α = 70.399 (11)°	µ = 1.12 mm⁻¹
β = 64.234 (10)°	T = 288 K
γ = 81.107 (10)°	Block, blue
V = 1006.5 (11) Å³	0.10 × 0.08 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3848 independent reflections
Radiation source: fine-focus sealed tube	3001 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
phi and ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS: Bruker, 1997)	h = −12→12
T_min = 0.898, T_max = 0.915	k = −13→10
5579 measured reflections	l = −13→9

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0506P)²] where P = (F_o² + 2F_c²)/3
3848 reflections	(Δ/σ)_max < 0.001
272 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Cu₂(C₇H₅O₂)₄(C₁₀H₉N)₂]	γ = 81.107 (10)°
M_r = 897.88	V = 1006.5 (11) Å³
Triclinic, P1	Z = 1
a = 10.420 (7) Å	Mo Kα radiation
b = 10.590 (7) Å	µ = 1.12 mm⁻¹
c = 10.751 (6) Å	T = 288 K
α = 70.399 (11)°	0.10 × 0.08 × 0.08 mm
β = 64.234 (10)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3848 independent reflections
Absorption correction: multi-scan (SADABS: Bruker, 1997)	3001 reflections with I > 2σ(I)
T_min = 0.898, T_max = 0.915	R_int = 0.021
5579 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.05	Δρ_max = 0.31 e Å⁻³
3848 reflections	Δρ_min = −0.33 e Å⁻³
272 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
Cu1	0.52984 (3)	0.89016 (3)	0.59215 (4)	0.03698 (14)
N1	0.6052 (2)	0.7261 (2)	0.7373 (2)	0.0381 (6)
C1	0.6560 (3)	0.7658 (3)	0.8104 (3)	0.0443 (7)
H1	0.6566	0.8574	0.7958	0.053*
C2	0.7091 (3)	0.6802 (3)	0.9084 (3)	0.0468 (8)
H2	0.7434	0.7144	0.9572	0.056*
C3	0.7097 (3)	0.5470 (3)	0.9310 (3)	0.0442 (7)
H3	0.7447	0.4885	0.9959	0.053*
C4	0.6576 (3)	0.4967 (3)	0.8567 (3)	0.0378 (7)
C5	0.6493 (3)	0.3595 (3)	0.8781 (3)	0.0449 (7)
H5	0.6834	0.2980	0.9421	0.054*
C6	0.5935 (3)	0.3131 (3)	0.8091 (3)	0.0442 (7)
C7	0.5463 (3)	0.4077 (3)	0.7091 (3)	0.0476 (8)
H7	0.5104	0.3775	0.6587	0.057*
C8	0.5519 (3)	0.5417 (3)	0.6840 (3)	0.0433 (7)
H8	0.5203	0.6016	0.6169	0.052*
C9	0.6053 (3)	0.5905 (3)	0.7591 (3)	0.0366 (6)
C10	0.5756 (4)	0.1656 (3)	0.8414 (4)	0.0595 (9)
H10A	0.6670	0.1251	0.8005	0.089*
H10B	0.5150	0.1533	0.8001	0.089*
H10C	0.5332	0.1243	0.9444	0.089*
O11	0.6763 (2)	1.01228 (19)	0.5543 (2)	0.0489 (5)
O12	0.3714 (2)	0.8060 (2)	0.5994 (2)	0.0487 (5)
C11	0.6982 (3)	1.1320 (3)	0.4734 (3)	0.0391 (7)
C12	0.8146 (3)	1.2041 (3)	0.4667 (3)	0.0383 (7)
C13	0.8366 (3)	1.3391 (3)	0.3937 (3)	0.0469 (8)
H13	0.7792	1.3862	0.3465	0.056*
C14	0.9423 (3)	1.4042 (3)	0.3903 (3)	0.0530 (8)
H14	0.9554	1.4954	0.3417	0.064*
C15	1.0290 (3)	1.3360 (3)	0.4580 (3)	0.0549 (9)
H15	1.1012	1.3805	0.4549	0.066*
C16	1.0084 (3)	1.2030 (3)	0.5295 (4)	0.0576 (9)
H16	1.0677	1.1561	0.5744	0.069*
C17	0.9012 (3)	1.1371 (3)	0.5361 (3)	0.0516 (8)
H17	0.8867	1.0465	0.5877	0.062*
O21	0.6535 (2)	0.8478 (2)	0.4116 (2)	0.0510 (6)
O22	0.3913 (2)	0.9690 (2)	0.7424 (2)	0.0487 (5)
C21	0.6732 (3)	0.9229 (3)	0.2858 (3)	0.0391 (7)
C22	0.7844 (3)	0.8779 (3)	0.1630 (3)	0.0409 (7)
C23	0.8502 (4)	0.7562 (4)	0.1888 (4)	0.0623 (10)
H23	0.8224	0.6991	0.2831	0.075*
C24	0.9574 (4)	0.7171 (4)	0.0763 (4)	0.0760 (12)
H24	1.0019	0.6341	0.0950	0.091*
C25	0.9985 (4)	0.8004 (4)	−0.0633 (4)	0.0680 (10)
H25	1.0712	0.7743	−0.1391	0.082*
C26	0.9323 (4)	0.9216 (4)	−0.0900 (4)	0.0617 (10)
H26	0.9594	0.9780	−0.1846	0.074*
C27	0.8256 (3)	0.9609 (3)	0.0223 (3)	0.0502 (8)
H27	0.7809	1.0438	0.0032	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0383 (2)	0.0324 (2)	0.0399 (2)	0.00153 (14)	−0.01945 (16)	−0.00685 (15)
N1	0.0415 (14)	0.0358 (14)	0.0372 (13)	0.0001 (10)	−0.0181 (11)	−0.0090 (10)
C1	0.0492 (18)	0.0365 (17)	0.0453 (18)	−0.0022 (13)	−0.0206 (15)	−0.0078 (13)
C2	0.0510 (19)	0.048 (2)	0.0507 (19)	−0.0009 (14)	−0.0295 (16)	−0.0147 (15)
C3	0.0407 (17)	0.0497 (19)	0.0418 (17)	0.0048 (14)	−0.0221 (14)	−0.0085 (14)
C4	0.0337 (16)	0.0377 (16)	0.0379 (16)	0.0021 (12)	−0.0144 (13)	−0.0079 (13)
C5	0.0423 (17)	0.0361 (17)	0.0494 (19)	0.0059 (13)	−0.0197 (15)	−0.0062 (14)
C6	0.0448 (18)	0.0392 (17)	0.0448 (18)	0.0036 (13)	−0.0168 (15)	−0.0120 (14)
C7	0.0540 (19)	0.0469 (19)	0.0497 (19)	0.0033 (15)	−0.0251 (16)	−0.0206 (15)
C8	0.0528 (19)	0.0393 (17)	0.0401 (17)	−0.0006 (14)	−0.0237 (15)	−0.0085 (13)
C9	0.0367 (16)	0.0363 (16)	0.0331 (15)	−0.0026 (12)	−0.0133 (13)	−0.0068 (12)
C10	0.073 (2)	0.0393 (19)	0.070 (2)	0.0016 (16)	−0.034 (2)	−0.0151 (16)
O11	0.0497 (13)	0.0358 (12)	0.0616 (14)	−0.0046 (9)	−0.0312 (11)	−0.0022 (10)
O12	0.0491 (13)	0.0398 (12)	0.0585 (13)	−0.0039 (10)	−0.0317 (11)	−0.0017 (10)
C11	0.0379 (16)	0.0363 (17)	0.0411 (17)	0.0006 (13)	−0.0132 (14)	−0.0137 (13)
C12	0.0350 (16)	0.0367 (16)	0.0413 (17)	0.0002 (12)	−0.0135 (13)	−0.0128 (13)
C13	0.0485 (19)	0.0387 (18)	0.0525 (19)	−0.0006 (14)	−0.0221 (16)	−0.0104 (14)
C14	0.058 (2)	0.0367 (18)	0.058 (2)	−0.0102 (15)	−0.0184 (17)	−0.0102 (15)
C15	0.0415 (19)	0.066 (2)	0.058 (2)	−0.0121 (16)	−0.0134 (16)	−0.0248 (18)
C16	0.048 (2)	0.060 (2)	0.069 (2)	−0.0029 (16)	−0.0319 (18)	−0.0124 (18)
C17	0.0471 (19)	0.0436 (19)	0.061 (2)	−0.0037 (15)	−0.0251 (17)	−0.0070 (15)
O21	0.0572 (14)	0.0438 (13)	0.0428 (13)	0.0113 (10)	−0.0182 (11)	−0.0104 (10)
O22	0.0509 (13)	0.0469 (13)	0.0484 (12)	0.0108 (10)	−0.0229 (10)	−0.0161 (10)
C21	0.0363 (16)	0.0394 (17)	0.0476 (19)	−0.0013 (13)	−0.0212 (14)	−0.0145 (14)
C22	0.0366 (16)	0.0488 (19)	0.0424 (18)	0.0003 (13)	−0.0196 (14)	−0.0158 (14)
C23	0.064 (2)	0.067 (2)	0.0436 (19)	0.0204 (18)	−0.0191 (18)	−0.0152 (17)
C24	0.070 (3)	0.082 (3)	0.068 (3)	0.037 (2)	−0.027 (2)	−0.032 (2)
C25	0.055 (2)	0.094 (3)	0.055 (2)	0.006 (2)	−0.0153 (19)	−0.036 (2)
C26	0.061 (2)	0.084 (3)	0.0413 (19)	−0.017 (2)	−0.0191 (18)	−0.0156 (18)
C27	0.053 (2)	0.053 (2)	0.050 (2)	−0.0023 (15)	−0.0265 (17)	−0.0140 (16)

Geometric parameters (Å, º) top

Cu1—O12	1.955 (2)	C11—O12ⁱ	1.254 (3)
Cu1—O21	1.964 (2)	C11—C12	1.495 (4)
Cu1—O11	1.971 (2)	C12—C13	1.380 (4)
Cu1—O22	1.974 (2)	C12—C17	1.381 (4)
Cu1—N1	2.212 (2)	C13—C14	1.367 (4)
Cu1—Cu1ⁱ	2.6939 (13)	C13—H13	0.9300
N1—C1	1.314 (4)	C14—C15	1.373 (4)
N1—C9	1.375 (4)	C14—H14	0.9300
C1—C2	1.396 (4)	C15—C16	1.359 (4)
C1—H1	0.9300	C15—H15	0.9300
C2—C3	1.347 (4)	C16—C17	1.370 (4)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.404 (4)	C17—H17	0.9300
C3—H3	0.9300	O21—C21	1.261 (3)
C4—C5	1.403 (4)	O22—C21ⁱ	1.250 (3)
C4—C9	1.419 (4)	C21—O22ⁱ	1.250 (3)
C5—C6	1.355 (4)	C21—C22	1.495 (4)
C5—H5	0.9300	C22—C23	1.364 (4)
C6—C7	1.410 (4)	C22—C27	1.380 (4)
C6—C10	1.505 (4)	C23—C24	1.379 (5)
C7—C8	1.358 (4)	C23—H23	0.9300
C7—H7	0.9300	C24—C25	1.372 (5)
C8—C9	1.410 (4)	C24—H24	0.9300
C8—H8	0.9300	C25—C26	1.363 (5)
C10—H10A	0.9600	C25—H25	0.9300
C10—H10B	0.9600	C26—C27	1.377 (5)
C10—H10C	0.9600	C26—H26	0.9300
O11—C11	1.262 (3)	C27—H27	0.9300
O12—C11ⁱ	1.254 (3)

O12—Cu1—O21	89.07 (10)	H10A—C10—H10C	109.5
O12—Cu1—O11	166.38 (8)	H10B—C10—H10C	109.5
O21—Cu1—O11	89.52 (10)	C11—O11—Cu1	127.61 (19)
O12—Cu1—O22	88.79 (10)	C11ⁱ—O12—Cu1	121.26 (19)
O21—Cu1—O22	166.32 (8)	O12ⁱ—C11—O11	124.7 (3)
O11—Cu1—O22	89.39 (10)	O12ⁱ—C11—C12	118.4 (3)
O12—Cu1—N1	101.96 (9)	O11—C11—C12	116.9 (3)
O21—Cu1—N1	97.02 (9)	C13—C12—C17	118.5 (3)
O11—Cu1—N1	91.66 (9)	C13—C12—C11	121.1 (3)
O22—Cu1—N1	96.64 (10)	C17—C12—C11	120.4 (3)
O12—Cu1—Cu1ⁱ	86.24 (7)	C14—C13—C12	120.4 (3)
O21—Cu1—Cu1ⁱ	82.33 (7)	C14—C13—H13	119.8
O11—Cu1—Cu1ⁱ	80.14 (7)	C12—C13—H13	119.8
O22—Cu1—Cu1ⁱ	84.05 (7)	C13—C14—C15	120.6 (3)
N1—Cu1—Cu1ⁱ	171.77 (6)	C13—C14—H14	119.7
C1—N1—C9	117.2 (2)	C15—C14—H14	119.7
C1—N1—Cu1	114.60 (19)	C16—C15—C14	119.3 (3)
C9—N1—Cu1	128.17 (19)	C16—C15—H15	120.4
N1—C1—C2	124.6 (3)	C14—C15—H15	120.4
N1—C1—H1	117.7	C15—C16—C17	120.7 (3)
C2—C1—H1	117.7	C15—C16—H16	119.6
C3—C2—C1	118.8 (3)	C17—C16—H16	119.6
C3—C2—H2	120.6	C16—C17—C12	120.5 (3)
C1—C2—H2	120.6	C16—C17—H17	119.8
C2—C3—C4	120.0 (3)	C12—C17—H17	119.8
C2—C3—H3	120.0	C21—O21—Cu1	125.3 (2)
C4—C3—H3	120.0	C21ⁱ—O22—Cu1	123.10 (19)
C5—C4—C3	123.6 (3)	O22ⁱ—C21—O21	125.0 (3)
C5—C4—C9	118.7 (3)	O22ⁱ—C21—C22	118.6 (3)
C3—C4—C9	117.7 (3)	O21—C21—C22	116.4 (3)
C6—C5—C4	122.6 (3)	C23—C22—C27	119.1 (3)
C6—C5—H5	118.7	C23—C22—C21	120.4 (3)
C4—C5—H5	118.7	C27—C22—C21	120.5 (3)
C5—C6—C7	118.0 (3)	C22—C23—C24	120.6 (3)
C5—C6—C10	121.9 (3)	C22—C23—H23	119.7
C7—C6—C10	120.1 (3)	C24—C23—H23	119.7
C8—C7—C6	121.9 (3)	C25—C24—C23	120.1 (4)
C8—C7—H7	119.0	C25—C24—H24	119.9
C6—C7—H7	119.0	C23—C24—H24	119.9
C7—C8—C9	120.3 (3)	C26—C25—C24	119.6 (3)
C7—C8—H8	119.8	C26—C25—H25	120.2
C9—C8—H8	119.8	C24—C25—H25	120.2
N1—C9—C8	119.9 (2)	C25—C26—C27	120.3 (3)
N1—C9—C4	121.7 (3)	C25—C26—H26	119.9
C8—C9—C4	118.4 (3)	C27—C26—H26	119.9
C6—C10—H10A	109.5	C26—C27—C22	120.3 (3)
C6—C10—H10B	109.5	C26—C27—H27	119.8
H10A—C10—H10B	109.5	C22—C27—H27	119.8
C6—C10—H10C	109.5

O12—Cu1—N1—C1	−147.0 (2)	Cu1ⁱ—Cu1—O12—C11ⁱ	1.0 (2)
O21—Cu1—N1—C1	122.5 (2)	Cu1—O11—C11—O12ⁱ	−0.8 (4)
O11—Cu1—N1—C1	32.8 (2)	Cu1—O11—C11—C12	178.41 (18)
O22—Cu1—N1—C1	−56.8 (2)	O12ⁱ—C11—C12—C13	6.2 (4)
O12—Cu1—N1—C9	33.2 (2)	O11—C11—C12—C13	−173.0 (3)
O21—Cu1—N1—C9	−57.3 (2)	O12ⁱ—C11—C12—C17	−175.0 (3)
O11—Cu1—N1—C9	−147.0 (2)	O11—C11—C12—C17	5.7 (4)
O22—Cu1—N1—C9	123.4 (2)	C17—C12—C13—C14	0.2 (5)
C9—N1—C1—C2	−0.3 (4)	C11—C12—C13—C14	179.0 (3)
Cu1—N1—C1—C2	179.9 (2)	C12—C13—C14—C15	0.7 (5)
N1—C1—C2—C3	0.2 (5)	C13—C14—C15—C16	−0.4 (5)
C1—C2—C3—C4	0.0 (5)	C14—C15—C16—C17	−0.9 (5)
C2—C3—C4—C5	−177.4 (3)	C15—C16—C17—C12	1.8 (5)
C2—C3—C4—C9	−0.1 (4)	C13—C12—C17—C16	−1.5 (5)
C3—C4—C5—C6	177.4 (3)	C11—C12—C17—C16	179.7 (3)
C9—C4—C5—C6	0.1 (4)	O12—Cu1—O21—C21	90.1 (2)
C4—C5—C6—C7	2.0 (5)	O11—Cu1—O21—C21	−76.4 (2)
C4—C5—C6—C10	−175.4 (3)	O22—Cu1—O21—C21	9.1 (5)
C5—C6—C7—C8	−1.9 (5)	N1—Cu1—O21—C21	−168.0 (2)
C10—C6—C7—C8	175.6 (3)	Cu1ⁱ—Cu1—O21—C21	3.8 (2)
C6—C7—C8—C9	−0.3 (5)	O12—Cu1—O22—C21ⁱ	−85.7 (2)
C1—N1—C9—C8	179.9 (3)	O21—Cu1—O22—C21ⁱ	−4.6 (5)
Cu1—N1—C9—C8	−0.3 (4)	O11—Cu1—O22—C21ⁱ	80.8 (2)
C1—N1—C9—C4	0.2 (4)	N1—Cu1—O22—C21ⁱ	172.4 (2)
Cu1—N1—C9—C4	−179.98 (18)	Cu1ⁱ—Cu1—O22—C21ⁱ	0.6 (2)
C7—C8—C9—N1	−177.4 (3)	Cu1—O21—C21—O22ⁱ	−5.7 (4)
C7—C8—C9—C4	2.3 (4)	Cu1—O21—C21—C22	173.24 (18)
C5—C4—C9—N1	177.5 (2)	O22ⁱ—C21—C22—C23	−175.4 (3)
C3—C4—C9—N1	0.0 (4)	O21—C21—C22—C23	5.6 (4)
C5—C4—C9—C8	−2.2 (4)	O22ⁱ—C21—C22—C27	6.9 (4)
C3—C4—C9—C8	−179.7 (3)	O21—C21—C22—C27	−172.1 (3)
O12—Cu1—O11—C11	−1.8 (5)	C27—C22—C23—C24	0.8 (5)
O21—Cu1—O11—C11	82.3 (3)	C21—C22—C23—C24	−177.0 (3)
O22—Cu1—O11—C11	−84.1 (3)	C22—C23—C24—C25	−0.3 (6)
N1—Cu1—O11—C11	179.3 (2)	C23—C24—C25—C26	−0.3 (6)
Cu1ⁱ—Cu1—O11—C11	0.0 (2)	C24—C25—C26—C27	0.5 (6)
O21—Cu1—O12—C11ⁱ	−81.4 (2)	C25—C26—C27—C22	−0.1 (5)
O11—Cu1—O12—C11ⁱ	2.7 (5)	C23—C22—C27—C26	−0.6 (5)
O22—Cu1—O12—C11ⁱ	85.1 (2)	C21—C22—C27—C26	177.2 (3)
N1—Cu1—O12—C11ⁱ	−178.4 (2)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O11	0.93	2.50	3.047 (4)	118
C2—H2···Cg1ⁱⁱ	0.93	2.82	3.734 (3)	168

Symmetry code: (ii) x, y, z+1.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₇H₅O₂)₄(C₁₀H₉N)₂]
M_r	897.88
Crystal system, space group	Triclinic, P1
Temperature (K)	288
a, b, c (Å)	10.420 (7), 10.590 (7), 10.751 (6)
α, β, γ (°)	70.399 (11), 64.234 (10), 81.107 (10)
V (Å³)	1006.5 (11)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.12
Crystal size (mm)	0.10 × 0.08 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS: Bruker, 1997)
T_min, T_max	0.898, 0.915
No. of measured, independent and observed [I > 2σ(I)] reflections	5579, 3848, 3001
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.100, 1.05
No. of reflections	3848
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.33

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), 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
C1—H1···O11	0.93	2.50	3.047 (4)	118
C2—H2···Cg1ⁱ	0.93	2.82	3.734 (3)	168

Symmetry code: (i) x, y, z+1.

π–π interactions ( Å, ° ) top

Cg2 is the centroid of ring C22–C27. The offset is defined as the distance between CgI and the perpendicular projection of CgJ on ring I.

CgI	CgJ	CgI···CgJ	Dihedral angle	Interplanar distance	Offset
Cg2	Cg2i	3.967 (4)	0	3.39	2.06

Symmetry code: (i) -x+2,-y+2,-z.

Acknowledgements

Financial support from the Environmental Technology Educational Innovation Program (2006) of the Ministry of Environment, the Cooperative Research Program for Agricultural Science and Technology Development (20070301–036-019–02), and the Seoul R&BD Program is gratefully acknowledged.

References

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