Tetra­kis(μ-2-phenyl­quinoline-4-carboxyl­ato-κ2O:O′)bis­[(methanol-κO)copper(II)]

Guo, J.; Yan, G.

doi:10.1107/S1600536812039839

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page m1296

https://doi.org/10.1107/S1600536812039839

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Tetrakis(μ-2-phenylquinoline-4-carboxylato-κ²O:O′)bis[(methanol-κO)copper(II)]

Junfang Guo ^a ^* and Guoping Yan ^a

^aSchool of Materials Science and Engineering, Wuhan Institute of Technology, 430073 Wuhan People's Republic of China
^*Correspondence e-mail: junfangguo@yahoo.com.cn

(Received 7 September 2012; accepted 19 September 2012; online 26 September 2012)

The title complex, [Cu₂(C₁₆H₁₀NO₂)₄(CH₃OH)₂], consists of centrosymmetric wheel-shaped dinuclear neutral molecules in which each Cu^II atom is coordinated in a slightly distorted square-pyramidal geometry by four O atoms of carboxylate groups from different ligands at the basal plane and an O atom of a methanol molecule at the axial position. In the crystal, the dinuclear complex molecules are linked into one-dimensional supramolecular columns parallel to the b axis by O—H⋯N hydrogen bonds and π–π stacking interactions [centroid–centroid distance = 3.7259 (11) Å].

Related literature

For the background to isonicotinic acid derivatives as polyfunctional ligands, see: Evans & Lin (2002 ); Aakeröy et al. (1999 ); Xiong et al. (2000 ); Qin et al. (2002 ); Shen et al. (2007 ). For the structures of related compounds, see: Bu et al. (2005 ); Wang et al. (2010 ); Ma & Lin (2008 ).

Experimental

Crystal data

[Cu₂(C₁₆H₁₀NO₂)₄(CH₄O)₂]
M_r = 1184.16
Triclinic, $[P \overline 1]$
a = 8.9671 (6) Å
b = 10.5859 (7) Å
c = 14.7767 (10) Å
α = 89.800 (1)°
β = 87.348 (1)°
γ = 77.300 (1)°
V = 1366.86 (16) Å³
Z = 1
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 293 K
0.31 × 0.24 × 0.17 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.780, T_max = 0.870
7266 measured reflections
4984 independent reflections
4583 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.088
S = 1.06
4984 reflections
370 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H1⋯N1ⁱ	0.83	1.95	2.784 (2)	176
Symmetry code: (i) x, y+1, z.

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); 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, global. DOI: https://doi.org/10.1107/S1600536812039839/rz5004sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812039839/rz5004Isup2.hkl

checkCIF report

Comment top

Isonicotinic acid and its derivatives, such as 9-acridinecarboxylic acid and 4-quinolinecarboxylic acid, bearing both neutral and anionic donor groups, have been widely used as polyfunctional ligands (Evans & Lin, 2002; Aakeröy et al., 1999; Xiong et al., 2000; Bu et al., 2005). 2-Phenylquinoline-4-carboxylic acid (HL), an analogue of isonicotinic acid, exhibits flexible ligation modes in the construction of diverse coordination motifs with unusual properties (Qin et al., 2002; Shen et al., 2007; Wang et al., 2010). Herein, we report a new copper(II) complex derived from 2-phenylquinoline-4-carboxylic acid.

The title complex shows a dinuclear paddle-wheel unit [Cu₂(L)₄(CH₃OH)₂] (Fig. 1), which is composed of two copper(II) ions, four L ligands and two methanol molecules. Each metal is pentacoordinated by four O atoms of the carboxylate groups from different ligands [Cu—O mean length = 1.961 (3) Å] at the equatorial plane and one O atom of a CH₃OH molecule at the axial position. One of the most common parameters used to define the coordination geometry of a pentacoordinated metal center, the τ index, is 0.0003, indicating an almost-ideal square-pyramidal coordination. The metal ion deviates from the mean equatorial plane of the square pyramid toward the apical O5 atom by 0.1942 (3) Å. The Cu···Cu distance is 2.6303 (5) Å, which is within the normal range observed for dinuclear paddle-wheel units in the structures of copper(II) carboxylate complexes (Bu et al., 2005; Wang et al., 2010; Ma & Lin, 2008). In the crystal (Fig. 2), the dinuclear complex molecules are linked into one-dimensional columns parallel to the b axis through intermolecular O—H···N hydrogen bonds (Table 1) and π–π stacking interactions involving adjacent quinoline rings, with centroid–centroid distances of 3.7259 (11) Å and perpendicular interplanar separations of 3.4838 (8) Å.

Related literature top

For background to isonicotinic acid derivatives as polyfunctional ligands, see Evans & Lin (2002); Aakeröy et al. (1999); Xiong et al. (2000); Qin et al. (2002); Shen et al. (2007). For the structures of related compounds, see Bu et al. (2005); Wang et al. (2010); Ma & Lin (2008).

Experimental top

2-Phenylquinoline-4-carboxylic acid (49.8 mg, 0.2 mmol) in CH₃OH/CHCl₃ solution (1:1 v/v, 25 ml) was added to a CH₃OH solution (25 ml) of Cu(NO₃)₂.2.5H₂O (46.5 mg, 0.2 mmol). The resulting solution was filtered and left to stand at room temperature. Green block-shaped single crystals suitable for X-ray analysis were obtained after several days (yield: 45%).

Structure description top

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by the symmetry code (-x+1, -y, -z+1).
	Fig. 2. Partial crystal packing of the title compound, showing the formation of a columnar supramolecular structure through hydrogen bonds (dashed lines).

Tetrakis(µ-2-phenylquinoline-4-carboxylato- κ²O:O')bis[(methanol-κO)copper(II)] top

Crystal data top

[Cu₂(C₁₆H₁₀NO₂)₄(CH₄O)₂]	Z = 1
M_r = 1184.16	F(000) = 610
Triclinic, P1	D_x = 1.439 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 8.9671 (6) Å	Cell parameters from 4273 reflections
b = 10.5859 (7) Å	θ = 2.7–25.5°
c = 14.7767 (10) Å	µ = 0.85 mm⁻¹
α = 89.800 (1)°	T = 293 K
β = 87.348 (1)°	Block, green
γ = 77.300 (1)°	0.31 × 0.24 × 0.17 mm
V = 1366.86 (16) Å³

Data collection top

Bruker APEX CCD diffractometer	4984 independent reflections
Radiation source: fine-focus sealed tube	4583 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
φ and ω scans	θ_max = 25.5°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
T_min = 0.780, T_max = 0.870	k = −10→12
7266 measured reflections	l = −17→14

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0453P)² + 0.8119P] where P = (F_o² + 2F_c²)/3
4984 reflections	(Δ/σ)_max = 0.002
370 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Cu₂(C₁₆H₁₀NO₂)₄(CH₄O)₂]	γ = 77.300 (1)°
M_r = 1184.16	V = 1366.86 (16) Å³
Triclinic, P1	Z = 1
a = 8.9671 (6) Å	Mo Kα radiation
b = 10.5859 (7) Å	µ = 0.85 mm⁻¹
c = 14.7767 (10) Å	T = 293 K
α = 89.800 (1)°	0.31 × 0.24 × 0.17 mm
β = 87.348 (1)°

Data collection top

Bruker APEX CCD diffractometer	4984 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	4583 reflections with I > 2σ(I)
T_min = 0.780, T_max = 0.870	R_int = 0.014
7266 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.06	Δρ_max = 0.48 e Å⁻³
4984 reflections	Δρ_min = −0.30 e Å⁻³
370 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3269 (2)	−0.31756 (19)	0.53165 (14)	0.0228 (4)
C2	0.3333 (2)	−0.40391 (19)	0.45686 (14)	0.0232 (4)
C3	0.2708 (2)	−0.51467 (19)	0.47299 (14)	0.0232 (4)
C4	0.2167 (2)	−0.4635 (2)	0.62569 (14)	0.0245 (4)
C5	0.2661 (2)	−0.3457 (2)	0.61337 (14)	0.0252 (4)
H5	0.2569	−0.2876	0.6614	0.030*
C6	0.3893 (2)	−0.3828 (2)	0.36841 (14)	0.0283 (5)
H6	0.4318	−0.3113	0.3570	0.034*
C7	0.3817 (3)	−0.4665 (2)	0.29958 (15)	0.0343 (5)
H7	0.4211	−0.4526	0.2420	0.041*
C8	0.3147 (3)	−0.5737 (2)	0.31503 (16)	0.0345 (5)
H8	0.3066	−0.6281	0.2671	0.041*
C9	0.2618 (2)	−0.5980 (2)	0.39974 (15)	0.0290 (5)
H9	0.2195	−0.6699	0.4095	0.035*
C10	0.1622 (2)	−0.5001 (2)	0.71649 (14)	0.0280 (5)
C11	0.2097 (3)	−0.6262 (2)	0.74798 (16)	0.0352 (5)
H11	0.2781	−0.6872	0.7126	0.042*
C12	0.1557 (3)	−0.6609 (2)	0.83149 (17)	0.0424 (6)
H12	0.1883	−0.7450	0.8524	0.051*
C13	0.0531 (3)	−0.5706 (3)	0.88392 (17)	0.0448 (6)
H13	0.0158	−0.5943	0.9397	0.054*
C14	0.0061 (3)	−0.4456 (3)	0.85373 (17)	0.0437 (6)
H14	−0.0631	−0.3853	0.8891	0.052*
C15	0.0617 (3)	−0.4093 (2)	0.77056 (16)	0.0348 (5)
H15	0.0317	−0.3242	0.7511	0.042*
C16	0.3837 (2)	−0.19459 (19)	0.52106 (13)	0.0224 (4)
C17	0.6511 (3)	−0.0701 (2)	0.75173 (14)	0.0278 (5)
C18	0.7991 (3)	−0.0616 (2)	0.77910 (15)	0.0302 (5)
C19	0.8346 (3)	−0.0995 (2)	0.86945 (15)	0.0319 (5)
C20	0.6033 (3)	−0.1580 (2)	0.89854 (15)	0.0312 (5)
C21	0.5550 (3)	−0.1164 (2)	0.81085 (15)	0.0299 (5)
H21	0.4578	−0.1209	0.7938	0.036*
C22	0.9081 (3)	−0.0138 (3)	0.72450 (17)	0.0404 (6)
H22	0.8868	0.0109	0.6652	0.049*
C23	1.0445 (3)	−0.0034 (3)	0.75807 (19)	0.0499 (7)
H23	1.1148	0.0287	0.7216	0.060*
C24	1.0790 (3)	−0.0408 (3)	0.84710 (19)	0.0492 (7)
H24	1.1718	−0.0328	0.8694	0.059*
C25	0.9774 (3)	−0.0891 (3)	0.90132 (17)	0.0419 (6)
H25	1.0026	−0.1153	0.9599	0.050*
C26	0.5958 (2)	−0.0336 (2)	0.65834 (14)	0.0261 (4)
C27	0.5007 (3)	−0.2130 (2)	0.96154 (16)	0.0369 (5)
C28	0.4088 (4)	−0.2913 (3)	0.9297 (2)	0.0595 (8)
H28	0.4114	−0.3103	0.8682	0.071*
C29	0.3129 (4)	−0.3413 (4)	0.9894 (2)	0.0801 (12)
H29	0.2533	−0.3954	0.9681	0.096*
C30	0.3061 (4)	−0.3108 (4)	1.0805 (2)	0.0723 (11)
H30	0.2397	−0.3424	1.1203	0.087*
C31	0.3971 (4)	−0.2339 (3)	1.1124 (2)	0.0565 (8)
H31	0.3928	−0.2142	1.1739	0.068*
C32	0.4952 (3)	−0.1857 (3)	1.05379 (17)	0.0436 (6)
H32	0.5577	−0.1347	1.0761	0.052*
C33	0.0245 (3)	0.1999 (3)	0.5450 (2)	0.0491 (7)
H33A	−0.0514	0.2706	0.5706	0.074*
H33B	−0.0003	0.1194	0.5629	0.074*
H33C	0.0268	0.2059	0.4801	0.074*
N1	0.21783 (19)	−0.54469 (16)	0.55746 (12)	0.0247 (4)
N2	0.7381 (2)	−0.14840 (18)	0.92751 (12)	0.0331 (4)
O1	0.29567 (17)	−0.09218 (14)	0.55023 (10)	0.0291 (3)
O2	0.51543 (16)	−0.20471 (13)	0.48438 (10)	0.0278 (3)
O3	0.46126 (18)	0.03347 (15)	0.65482 (10)	0.0324 (4)
O4	0.68533 (17)	−0.07591 (14)	0.59207 (10)	0.0290 (3)
O5	0.17001 (16)	0.20531 (13)	0.57646 (10)	0.0267 (3)
H1	0.1821	0.2812	0.5735	0.040*
Cu1	0.37041 (3)	0.06756 (2)	0.536332 (16)	0.02076 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0185 (10)	0.0188 (10)	0.0312 (11)	−0.0041 (8)	−0.0020 (8)	0.0042 (8)
C2	0.0184 (10)	0.0210 (10)	0.0294 (11)	−0.0027 (8)	−0.0018 (8)	0.0023 (8)
C3	0.0211 (10)	0.0192 (10)	0.0289 (11)	−0.0039 (8)	−0.0009 (8)	0.0037 (8)
C4	0.0215 (10)	0.0228 (10)	0.0294 (11)	−0.0054 (8)	0.0007 (8)	0.0041 (9)
C5	0.0249 (10)	0.0215 (10)	0.0300 (11)	−0.0072 (8)	0.0002 (8)	−0.0004 (8)
C6	0.0291 (11)	0.0263 (11)	0.0306 (11)	−0.0087 (9)	0.0003 (9)	0.0064 (9)
C7	0.0412 (13)	0.0353 (13)	0.0270 (11)	−0.0105 (10)	0.0009 (10)	0.0058 (10)
C8	0.0444 (14)	0.0293 (12)	0.0307 (12)	−0.0092 (10)	−0.0045 (10)	−0.0011 (9)
C9	0.0319 (12)	0.0217 (11)	0.0346 (12)	−0.0084 (9)	−0.0024 (9)	0.0014 (9)
C10	0.0296 (11)	0.0281 (11)	0.0295 (11)	−0.0138 (9)	0.0000 (9)	0.0024 (9)
C11	0.0423 (13)	0.0311 (12)	0.0334 (12)	−0.0110 (10)	0.0007 (10)	0.0048 (10)
C12	0.0583 (16)	0.0334 (13)	0.0397 (14)	−0.0194 (12)	−0.0022 (12)	0.0114 (11)
C13	0.0576 (16)	0.0556 (17)	0.0287 (12)	−0.0297 (14)	0.0042 (11)	0.0051 (11)
C14	0.0470 (15)	0.0501 (16)	0.0350 (13)	−0.0152 (12)	0.0101 (11)	−0.0041 (12)
C15	0.0375 (13)	0.0330 (12)	0.0343 (12)	−0.0090 (10)	0.0020 (10)	0.0009 (10)
C16	0.0232 (10)	0.0210 (10)	0.0238 (10)	−0.0066 (8)	−0.0026 (8)	0.0043 (8)
C17	0.0334 (12)	0.0252 (11)	0.0253 (11)	−0.0071 (9)	−0.0021 (9)	−0.0008 (9)
C18	0.0335 (12)	0.0291 (12)	0.0292 (11)	−0.0094 (9)	−0.0018 (9)	−0.0017 (9)
C19	0.0353 (12)	0.0314 (12)	0.0297 (12)	−0.0085 (10)	−0.0021 (9)	−0.0012 (9)
C20	0.0343 (12)	0.0312 (12)	0.0275 (11)	−0.0062 (10)	−0.0012 (9)	0.0023 (9)
C21	0.0323 (12)	0.0311 (12)	0.0277 (11)	−0.0094 (9)	−0.0027 (9)	0.0010 (9)
C22	0.0442 (14)	0.0494 (15)	0.0327 (13)	−0.0213 (12)	−0.0010 (10)	0.0026 (11)
C23	0.0461 (15)	0.0695 (19)	0.0427 (15)	−0.0320 (14)	0.0009 (12)	0.0010 (13)
C24	0.0397 (14)	0.0660 (19)	0.0484 (16)	−0.0247 (13)	−0.0077 (12)	−0.0021 (14)
C25	0.0427 (14)	0.0529 (16)	0.0327 (13)	−0.0145 (12)	−0.0095 (11)	−0.0011 (11)
C26	0.0336 (12)	0.0224 (10)	0.0256 (11)	−0.0129 (9)	−0.0026 (9)	0.0018 (8)
C27	0.0363 (13)	0.0426 (14)	0.0313 (12)	−0.0074 (11)	−0.0031 (10)	0.0125 (10)
C28	0.0622 (19)	0.086 (2)	0.0424 (16)	−0.0414 (17)	−0.0137 (14)	0.0240 (15)
C29	0.070 (2)	0.128 (3)	0.065 (2)	−0.066 (2)	−0.0248 (17)	0.046 (2)
C30	0.0505 (18)	0.112 (3)	0.061 (2)	−0.0313 (19)	−0.0030 (15)	0.049 (2)
C31	0.0649 (19)	0.0587 (18)	0.0397 (15)	−0.0031 (15)	0.0116 (14)	0.0182 (13)
C32	0.0526 (16)	0.0404 (14)	0.0356 (13)	−0.0065 (12)	0.0034 (11)	0.0096 (11)
C33	0.0239 (12)	0.0522 (16)	0.0721 (19)	−0.0098 (11)	−0.0035 (12)	0.0147 (14)
N1	0.0232 (9)	0.0217 (9)	0.0299 (9)	−0.0066 (7)	0.0005 (7)	0.0035 (7)
N2	0.0389 (11)	0.0341 (11)	0.0266 (10)	−0.0081 (9)	−0.0031 (8)	0.0025 (8)
O1	0.0305 (8)	0.0200 (7)	0.0375 (9)	−0.0089 (6)	0.0078 (6)	0.0006 (6)
O2	0.0236 (7)	0.0204 (7)	0.0407 (9)	−0.0085 (6)	0.0020 (6)	0.0017 (6)
O3	0.0341 (9)	0.0381 (9)	0.0232 (8)	−0.0040 (7)	−0.0006 (6)	0.0037 (7)
O4	0.0327 (8)	0.0311 (8)	0.0232 (7)	−0.0068 (7)	−0.0026 (6)	0.0011 (6)
O5	0.0229 (7)	0.0185 (7)	0.0385 (8)	−0.0044 (6)	−0.0001 (6)	0.0005 (6)
Cu1	0.02186 (14)	0.01805 (14)	0.02282 (14)	−0.00599 (10)	0.00180 (9)	0.00185 (9)

Geometric parameters (Å, º) top

C1—C5	1.361 (3)	C20—N2	1.325 (3)
C1—C2	1.428 (3)	C20—C21	1.423 (3)
C1—C16	1.504 (3)	C20—C27	1.485 (3)
C2—C6	1.413 (3)	C21—H21	0.9300
C2—C3	1.421 (3)	C22—C23	1.367 (4)
C3—N1	1.376 (3)	C22—H22	0.9300
C3—C9	1.415 (3)	C23—C24	1.401 (4)
C4—N1	1.325 (3)	C23—H23	0.9300
C4—C5	1.421 (3)	C24—C25	1.367 (4)
C4—C10	1.486 (3)	C24—H24	0.9300
C5—H5	0.9300	C25—H25	0.9300
C6—C7	1.365 (3)	C26—O4	1.256 (3)
C6—H6	0.9300	C26—O3	1.261 (3)
C7—C8	1.409 (3)	C27—C28	1.388 (4)
C7—H7	0.9300	C27—C32	1.391 (3)
C8—C9	1.362 (3)	C28—C29	1.387 (4)
C8—H8	0.9300	C28—H28	0.9300
C9—H9	0.9300	C29—C30	1.380 (5)
C10—C15	1.390 (3)	C29—H29	0.9300
C10—C11	1.394 (3)	C30—C31	1.372 (5)
C11—C12	1.383 (3)	C30—H30	0.9300
C11—H11	0.9300	C31—C32	1.381 (4)
C12—C13	1.383 (4)	C31—H31	0.9300
C12—H12	0.9300	C32—H32	0.9300
C13—C14	1.377 (4)	C33—O5	1.418 (3)
C13—H13	0.9300	C33—H33A	0.9600
C14—C15	1.390 (3)	C33—H33B	0.9600
C14—H14	0.9300	C33—H33C	0.9600
C15—H15	0.9300	O1—Cu1	1.9581 (14)
C16—O1	1.257 (2)	O2—Cu1ⁱ	1.9674 (13)
C16—O2	1.260 (2)	O3—Cu1	1.9641 (15)
C17—C21	1.363 (3)	O4—Cu1ⁱ	1.9812 (14)
C17—C18	1.427 (3)	O5—Cu1	2.1125 (14)
C17—C26	1.508 (3)	O5—H1	0.8340
C18—C22	1.416 (3)	Cu1—O2ⁱ	1.9674 (14)
C18—C19	1.423 (3)	Cu1—O4ⁱ	1.9812 (14)
C19—N2	1.370 (3)	Cu1—Cu1ⁱ	2.6303 (5)
C19—C25	1.411 (3)

C5—C1—C2	119.56 (18)	C23—C22—C18	120.7 (2)
C5—C1—C16	119.45 (18)	C23—C22—H22	119.7
C2—C1—C16	120.98 (17)	C18—C22—H22	119.7
C6—C2—C3	118.79 (19)	C22—C23—C24	120.4 (2)
C6—C2—C1	124.56 (18)	C22—C23—H23	119.8
C3—C2—C1	116.57 (18)	C24—C23—H23	119.8
N1—C3—C9	118.14 (18)	C25—C24—C23	120.5 (2)
N1—C3—C2	122.63 (18)	C25—C24—H24	119.8
C9—C3—C2	119.23 (19)	C23—C24—H24	119.8
N1—C4—C5	121.68 (19)	C24—C25—C19	120.7 (2)
N1—C4—C10	117.63 (18)	C24—C25—H25	119.6
C5—C4—C10	120.69 (19)	C19—C25—H25	119.6
C1—C5—C4	120.35 (19)	O4—C26—O3	126.5 (2)
C1—C5—H5	119.8	O4—C26—C17	117.32 (19)
C4—C5—H5	119.8	O3—C26—C17	116.17 (19)
C7—C6—C2	120.5 (2)	C28—C27—C32	119.1 (2)
C7—C6—H6	119.7	C28—C27—C20	120.9 (2)
C2—C6—H6	119.7	C32—C27—C20	120.0 (2)
C6—C7—C8	120.6 (2)	C29—C28—C27	120.2 (3)
C6—C7—H7	119.7	C29—C28—H28	119.9
C8—C7—H7	119.7	C27—C28—H28	119.9
C9—C8—C7	120.4 (2)	C30—C29—C28	120.0 (3)
C9—C8—H8	119.8	C30—C29—H29	120.0
C7—C8—H8	119.8	C28—C29—H29	120.0
C8—C9—C3	120.4 (2)	C31—C30—C29	120.0 (3)
C8—C9—H9	119.8	C31—C30—H30	120.0
C3—C9—H9	119.8	C29—C30—H30	120.0
C15—C10—C11	119.2 (2)	C30—C31—C32	120.4 (3)
C15—C10—C4	120.3 (2)	C30—C31—H31	119.8
C11—C10—C4	120.4 (2)	C32—C31—H31	119.8
C12—C11—C10	120.3 (2)	C31—C32—C27	120.2 (3)
C12—C11—H11	119.8	C31—C32—H32	119.9
C10—C11—H11	119.8	C27—C32—H32	119.9
C11—C12—C13	120.0 (2)	O5—C33—H33A	109.5
C11—C12—H12	120.0	O5—C33—H33B	109.5
C13—C12—H12	120.0	H33A—C33—H33B	109.5
C14—C13—C12	120.2 (2)	O5—C33—H33C	109.5
C14—C13—H13	119.9	H33A—C33—H33C	109.5
C12—C13—H13	119.9	H33B—C33—H33C	109.5
C13—C14—C15	120.2 (2)	C4—N1—C3	118.90 (17)
C13—C14—H14	119.9	C20—N2—C19	118.18 (19)
C15—C14—H14	119.9	C16—O1—Cu1	116.67 (13)
C14—C15—C10	120.0 (2)	C16—O2—Cu1ⁱ	128.06 (13)
C14—C15—H15	120.0	C26—O3—Cu1	119.04 (14)
C10—C15—H15	120.0	C26—O4—Cu1ⁱ	125.28 (14)
O1—C16—O2	126.46 (18)	C33—O5—Cu1	122.05 (15)
O1—C16—C1	116.89 (17)	C33—O5—H1	109.7
O2—C16—C1	116.64 (17)	Cu1—O5—H1	112.6
C21—C17—C18	119.5 (2)	O1—Cu1—O3	88.25 (7)
C21—C17—C26	117.53 (19)	O1—Cu1—O2ⁱ	168.60 (6)
C18—C17—C26	122.98 (19)	O3—Cu1—O2ⁱ	89.51 (6)
C22—C18—C19	118.7 (2)	O1—Cu1—O4ⁱ	89.50 (6)
C22—C18—C17	124.8 (2)	O3—Cu1—O4ⁱ	168.63 (6)
C19—C18—C17	116.4 (2)	O2ⁱ—Cu1—O4ⁱ	90.51 (6)
N2—C19—C25	117.6 (2)	O1—Cu1—O5	100.09 (6)
N2—C19—C18	123.4 (2)	O3—Cu1—O5	99.20 (6)
C25—C19—C18	119.0 (2)	O2ⁱ—Cu1—O5	91.30 (6)
N2—C20—C21	122.3 (2)	O4ⁱ—Cu1—O5	92.17 (6)
N2—C20—C27	117.7 (2)	O1—Cu1—Cu1ⁱ	89.46 (4)
C21—C20—C27	120.0 (2)	O3—Cu1—Cu1ⁱ	87.46 (5)
C17—C21—C20	120.1 (2)	O2ⁱ—Cu1—Cu1ⁱ	79.27 (4)
C17—C21—H21	119.9	O4ⁱ—Cu1—Cu1ⁱ	81.37 (5)
C20—C21—H21	119.9	O5—Cu1—Cu1ⁱ	168.47 (4)

C5—C1—C2—C6	178.0 (2)	C23—C24—C25—C19	−1.4 (4)
C16—C1—C2—C6	−0.9 (3)	N2—C19—C25—C24	−179.8 (2)
C5—C1—C2—C3	1.4 (3)	C18—C19—C25—C24	1.3 (4)
C16—C1—C2—C3	−177.41 (17)	C21—C17—C26—O4	−131.5 (2)
C6—C2—C3—N1	178.03 (19)	C18—C17—C26—O4	46.7 (3)
C1—C2—C3—N1	−5.2 (3)	C21—C17—C26—O3	46.2 (3)
C6—C2—C3—C9	−2.1 (3)	C18—C17—C26—O3	−135.6 (2)
C1—C2—C3—C9	174.67 (18)	N2—C20—C27—C28	−143.6 (3)
C2—C1—C5—C4	3.3 (3)	C21—C20—C27—C28	37.0 (4)
C16—C1—C5—C4	−177.83 (18)	N2—C20—C27—C32	36.8 (3)
N1—C4—C5—C1	−4.8 (3)	C21—C20—C27—C32	−142.6 (2)
C10—C4—C5—C1	174.91 (19)	C32—C27—C28—C29	0.0 (5)
C3—C2—C6—C7	0.8 (3)	C20—C27—C28—C29	−179.6 (3)
C1—C2—C6—C7	−175.6 (2)	C27—C28—C29—C30	1.5 (6)
C2—C6—C7—C8	1.4 (3)	C28—C29—C30—C31	−1.8 (6)
C6—C7—C8—C9	−2.5 (4)	C29—C30—C31—C32	0.5 (5)
C7—C8—C9—C3	1.2 (3)	C30—C31—C32—C27	1.0 (4)
N1—C3—C9—C8	−179.0 (2)	C28—C27—C32—C31	−1.2 (4)
C2—C3—C9—C8	1.1 (3)	C20—C27—C32—C31	178.4 (2)
N1—C4—C10—C15	−135.3 (2)	C5—C4—N1—C3	1.1 (3)
C5—C4—C10—C15	45.0 (3)	C10—C4—N1—C3	−178.63 (18)
N1—C4—C10—C11	44.0 (3)	C9—C3—N1—C4	−175.89 (19)
C5—C4—C10—C11	−135.8 (2)	C2—C3—N1—C4	4.0 (3)
C15—C10—C11—C12	1.0 (3)	C21—C20—N2—C19	−1.6 (3)
C4—C10—C11—C12	−178.3 (2)	C27—C20—N2—C19	179.0 (2)
C10—C11—C12—C13	0.5 (4)	C25—C19—N2—C20	179.6 (2)
C11—C12—C13—C14	−0.8 (4)	C18—C19—N2—C20	−1.6 (3)
C12—C13—C14—C15	−0.2 (4)	O2—C16—O1—Cu1	0.5 (3)
C13—C14—C15—C10	1.6 (4)	C1—C16—O1—Cu1	179.94 (13)
C11—C10—C15—C14	−2.0 (3)	O1—C16—O2—Cu1ⁱ	2.0 (3)
C4—C10—C15—C14	177.2 (2)	C1—C16—O2—Cu1ⁱ	−177.45 (13)
C5—C1—C16—O1	−48.6 (3)	O4—C26—O3—Cu1	5.0 (3)
C2—C1—C16—O1	130.2 (2)	C17—C26—O3—Cu1	−172.51 (13)
C5—C1—C16—O2	130.9 (2)	O3—C26—O4—Cu1ⁱ	−8.3 (3)
C2—C1—C16—O2	−50.3 (3)	C17—C26—O4—Cu1ⁱ	169.13 (13)
C21—C17—C18—C22	−179.1 (2)	C16—O1—Cu1—O3	−89.21 (15)
C26—C17—C18—C22	2.7 (4)	C16—O1—Cu1—O2ⁱ	−10.4 (4)
C21—C17—C18—C19	−1.8 (3)	C16—O1—Cu1—O4ⁱ	79.64 (15)
C26—C17—C18—C19	179.97 (19)	C16—O1—Cu1—O5	171.75 (15)
C22—C18—C19—N2	−179.2 (2)	C16—O1—Cu1—Cu1ⁱ	−1.74 (15)
C17—C18—C19—N2	3.3 (3)	C26—O3—Cu1—O1	89.18 (16)
C22—C18—C19—C25	−0.4 (3)	C26—O3—Cu1—O2ⁱ	−79.64 (16)
C17—C18—C19—C25	−177.9 (2)	C26—O3—Cu1—O4ⁱ	10.5 (4)
C18—C17—C21—C20	−1.1 (3)	C26—O3—Cu1—O5	−170.88 (15)
C26—C17—C21—C20	177.21 (19)	C26—O3—Cu1—Cu1ⁱ	−0.36 (15)
N2—C20—C21—C17	3.0 (3)	C33—O5—Cu1—O1	−45.20 (18)
C27—C20—C21—C17	−177.7 (2)	C33—O5—Cu1—O3	−135.05 (17)
C19—C18—C22—C23	−0.4 (4)	C33—O5—Cu1—O2ⁱ	135.23 (17)
C17—C18—C22—C23	176.8 (2)	C33—O5—Cu1—O4ⁱ	44.68 (17)
C18—C22—C23—C24	0.4 (4)	C33—O5—Cu1—Cu1ⁱ	100.3 (2)
C22—C23—C24—C25	0.5 (5)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···N1ⁱⁱ	0.83	1.95	2.784 (2)	176

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

Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₆H₁₀NO₂)₄(CH₄O)₂]
M_r	1184.16
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.9671 (6), 10.5859 (7), 14.7767 (10)
α, β, γ (°)	89.800 (1), 87.348 (1), 77.300 (1)
V (Å³)	1366.86 (16)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.31 × 0.24 × 0.17

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.780, 0.870
No. of measured, independent and observed [I > 2σ(I)] reflections	7266, 4984, 4583
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.088, 1.06
No. of reflections	4984
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.30

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), 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
O5—H1···N1ⁱ	0.83	1.95	2.784 (2)	176

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

Acknowledgements

The work described in this paper was supported by grants from the National Natural Science Foundation of China (NSFC 21001085), the Hubei Province Natural Science Foundation (2010CDB11104), and the Doctoral Program Foundation of Wuhan Institute of Technology (11105032).

References

Aakeröy, C., Beatty, A. & Leinen, D. (1999). Angew. Chem. Int. Ed. 38, 1815–1819. Google Scholar
Bruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison , Wisconsin , USA . Google Scholar
Bu, X., Tong, M., Xie, Y., Li, J., Chang, H., Kitagawa, S. & Ribas, J. (2005). Inorg. Chem. 44, 9837–9846. Web of Science CSD CrossRef PubMed CAS Google Scholar
Evans, O. & Lin, W. (2002). Acc. Chem. Res. 35, 511–522. Web of Science CrossRef PubMed CAS Google Scholar
Ma, L. & Lin, W. (2008). J. Am. Chem. Soc. 130, 13834–13835. Web of Science CSD CrossRef PubMed CAS Google Scholar
Qin, Z., Jennings, M., Puddephatt, R. & Muir, K. (2002). Inorg. Chem. 41, 5174–5186. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shen, Y., Li, Z., Cheng, J., Qin, Y. & Yao, Y. (2007). Inorg. Chem. Commun. 10, 888–890. Web of Science CSD CrossRef CAS Google Scholar
Wang, J., Chang, Z., Zhang, A., Hu, T. & Bu, X. (2010). Inorg. Chim. Acta, 363, 1377–1385. Web of Science CSD CrossRef CAS Google Scholar
Xiong, R., Zuo, J., You, X., Fun, H. & Raj, S. (2000). Organometallics, 19, 4183–4186. Web of Science CSD CrossRef CAS Google Scholar

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