Bis(μ-biphenyl-2,2′-dicarboxyl­ato)bis­[(2,2′-bipyridine)copper(II)]

Guo, H.-X.; Liang, M.; Lin, B.; Wang, Q.-H.; Li, X.-Z.

doi:10.1107/S160053680802583X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Pages m1171-m1172

doi:10.1107/S160053680802583X

Open

access

Bis(μ-biphenyl-2,2′-dicarboxylato)bis[(2,2′-bipyridine)copper(II)]

Hong-Xu Guo,^a ^* Min Liang,^a Bin Lin,^a Qing-Hua Wang ^a and Xi-Zhong Li ^a

^aDepartment of Chemistry and Environmental Science, Zhangzhou Normal University, Zhangzhou, Fujian 363000, People's Republic of China
^*Correspondence e-mail: ghx919@yahoo.com.cn

(Received 3 August 2008; accepted 11 August 2008; online 16 August 2008)

The title compound, [Cu₂(C₁₄H₈O₄)₂(C₁₀H₈N₂)₂], is a centrosymmetric binuclear copper(II) complex, with a Cu⋯Cu separation of 6.136 (16) Å. The Cu atom displays a cis-CuN₂O₂ square-planar geometry, although two long (> 2.43 Å) Cu⋯O contacts complete a distorted cis-CuN₂O₄ octahedron. Extensive C—H⋯O hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For related literature, see: Bu et al. (2004 ); He et al. (2007 ); Huang et al. (2004 ); Long et al. (2001 ); Ma et al. (2003 ); Rao et al. (2004 ); Yaghi et al. (2003 ); Yang et al. (2002 ); Zhang et al. (2004 ); Zhu et al. (2001 ); He & Zhu (2003 ).

Experimental

Crystal data

[Cu₂(C₁₄H₈O₄)₂(C₁₀H₈N₂)₂]
M_r = 1839.75
Monoclinic, P 2₁ /c
a = 11.234 (2) Å
b = 13.336 (3) Å
c = 15.431 (6) Å
β = 122.16 (2)°
V = 1957.1 (9) Å³
Z = 2
Mo Kα radiation
μ = 1.15 mm⁻¹
T = 293 (2) K
0.40 × 0.26 × 0.23 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.708, T_max = 0.771
18687 measured reflections
4472 independent reflections
3708 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.118
S = 1.03
4472 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.9640 (15)
Cu1—O4ⁱ	1.9725 (16)
Cu1—N2	1.9814 (19)
Cu1—N1	1.9897 (19)
Cu1—O2	2.434 (2)
Cu1—O3ⁱ	2.557 (2)

O1—Cu1—O4ⁱ	93.92 (7)
O1—Cu1—N2	162.77 (7)
O4ⁱ—Cu1—N2	95.38 (8)
O1—Cu1—N1	94.56 (7)
O4ⁱ—Cu1—N1	160.15 (7)
N2—Cu1—N1	81.35 (8)
Symmetry code: (i) -x+1, -y, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1	0.93	2.58	3.081 (3)	114
C4—H4A⋯O4ⁱⁱ	0.93	2.59	3.378 (3)	143
C5—H5A⋯O4ⁱⁱ	0.93	2.51	3.304 (4)	144
C6—H6A⋯O3ⁱⁱⁱ	0.93	2.25	3.162 (3)	166
C16—H16A⋯O2^iv	0.93	2.48	3.192 (3)	133
C19—H19A⋯O4	0.93	2.45	2.761 (3)	100
Symmetry codes: (ii) $[-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (iii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1994 ); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680802583X/om2255sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680802583X/om2255Isup2.hkl

checkCIF report

Comment top

Design and assembly of metal-involved supramolecular architectures are currently of great interest in the field of supramolecular chemistry and crystal engineering because they can provide novel topology and functional materials (Yaghi et al.,2003; Rao et al.,2004). During the past decades, extensive efforts have been focused on the design and assembly of such kinds of supramolecular architectures (Huang et al.,2004; Zhang et al., 2004). By precisely selecting the modular building unit, chemists now have successfully synthesized a great variety of one-dimensional, two-dimensional, and three-dimensional supramolecular architectures (Bu et al., 2004; Ma et al., 2003; Yang et al., 2002; Long et al., 2001). Binuclear copper(II) complexes have been intensely investigated owing to their potential application as magnetic materials and catalysts (Zhu et al., 2001).In this work, we employed H₂dpa (dpa = diphenyl-2,2'-dicarboxylato dianion) and 2,2'-bipyridine(bipy) ligands for producing a binuclear complex, [Cu₂(C₁₄H₈O₄)₂(C₁₀H₈N₂)₂].

The compound contains a centrosymmetric binuclear complex. The copper(II) atom in the title compound adopts a distorted square geometry (Table 1, Fig. 1). The bipy ligand shows its classical bidentate coordination mode, with a similar Cu—N bond length to that the related complex [Cu₂(C₁₄H₈O₄)₂(C₁₀H₈N₂)₂].4H₂O (He et al., 2007). The dpa ligand adopts a µ-bridged coordination and the dihedral angle between its aromatic rings is 78.27°. As well as the short Cu—O bonds, two long Cu—O (Cu(1)—O(2): 2.434 (44) Å; Cu(1)—O(3):2.557 (31) Å) contacts that might be regarded as secondary bonds (He & Zhu, 2003) complete a distorted octahedron. The Cu···Cuⁱ (i = 1 - x, -y, -z) distance bridged by the dpa ligands is 6.136 (16) Å. Extensive C—H···O hydrogen bonds link molecules into a three-dimensional network.(Table 2, Fig.2).

Related literature top

For related literature, see: Bu et al. (2004); He et al. (2007); Huang et al. (2004); Long et al. (2001); Ma et al. (2003); Rao et al. (2004); Yaghi et al. (2003); Yang et al. (2002); Zhang et al. (2004); Zhu et al. (2001); He & Zhu (2003).

Experimental top

A solution of Cu(NO₃)₂.6H₂O(0.0705 g) in 5 ml of water was added dropwise under continuous stirring to an aqueous solution (5 ml) of diphenyl-2,2'-dicarboxylic acid (0.0734 g) and 2,2'-bipyridine (0.0312 g). The resulting mixture was then transferred into a 25 ml Teflon-lined stainless steel vessel, which was sealed and heated to 423 K for 72 h, then cooled to room temperature. The block blue single crystals were obtained.

Computing details top

Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the structure of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level; H-atoms are shown as small spheres of arbitrary radius.
	Fig. 2. View of the 3D hydrogen-bonded network in the packing of the title compound.The packing is viewed along the b axis; C—H···O interactions are shown as dashed lines.

Bis(µ-biphenyl-2,2'-dicarboxylato)bis[(2,2'-bipyridine)copper(II)] top

Crystal data top

[Cu₂(C₁₄H₈O₄)₂(C₁₀H₈N₂)₂]	F(000) = 940
M_r = 1839.75	D_x = 1.561 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 19150 reflections
a = 11.234 (2) Å	θ = 3.1–27.4°
b = 13.336 (3) Å	µ = 1.15 mm⁻¹
c = 15.431 (6) Å	T = 293 K
β = 122.16 (2)°	Block, blue
V = 1957.1 (9) Å³	0.40 × 0.26 × 0.23 mm
Z = 2

Data collection top

Siemens SMART CCD area-detector diffractometer	4472 independent reflections
Radiation source: fine-focus sealed tube	3708 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω scans	θ_max = 27.4°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.708, T_max = 0.771	k = −17→17
18687 measured reflections	l = −18→19

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.08P)²] where P = (F_o² + 2F_c²)/3
4472 reflections	(Δ/σ)_max = 0.001
280 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

[Cu₂(C₁₄H₈O₄)₂(C₁₀H₈N₂)₂]	V = 1957.1 (9) Å³
M_r = 1839.75	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.234 (2) Å	µ = 1.15 mm⁻¹
b = 13.336 (3) Å	T = 293 K
c = 15.431 (6) Å	0.40 × 0.26 × 0.23 mm
β = 122.16 (2)°

Data collection top

Siemens SMART CCD area-detector diffractometer	4472 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3708 reflections with I > 2σ(I)
T_min = 0.708, T_max = 0.771	R_int = 0.046
18687 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.04	Δρ_max = 0.29 e Å⁻³
4472 reflections	Δρ_min = −0.60 e Å⁻³
280 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	0.63909 (3)	−0.160660 (19)	−0.059678 (18)	0.02914 (12)
O1	0.70349 (16)	−0.04363 (11)	0.03157 (11)	0.0354 (4)
O2	0.8638 (2)	−0.16096 (12)	0.10287 (15)	0.0530 (5)
O3	0.62962 (19)	0.15631 (14)	0.16045 (14)	0.0480 (5)
O4	0.47467 (16)	0.21452 (12)	0.00754 (11)	0.0374 (4)
N1	0.68794 (18)	−0.10223 (14)	−0.15551 (13)	0.0320 (4)
N2	0.63566 (18)	−0.28542 (14)	−0.13069 (14)	0.0331 (4)
C1	0.7186 (2)	−0.00573 (19)	−0.15928 (18)	0.0406 (5)
H1A	0.7227	0.0390	−0.1115	0.049*
C2	0.7441 (3)	0.0289 (2)	−0.2320 (2)	0.0504 (7)
H2A	0.7664	0.0959	−0.2327	0.060*
C3	0.7361 (3)	−0.0368 (2)	−0.3032 (2)	0.0531 (7)
H3A	0.7514	−0.0145	−0.3536	0.064*
C4	0.7051 (3)	−0.1367 (2)	−0.29961 (19)	0.0462 (6)
H4A	0.7002	−0.1823	−0.3470	0.055*
C5	0.6486 (3)	−0.3529 (2)	−0.2682 (2)	0.0487 (7)
H5A	0.6566	−0.3429	−0.3246	0.058*
C6	0.6319 (3)	−0.4472 (2)	−0.2420 (3)	0.0585 (8)
H6A	0.6296	−0.5022	−0.2800	0.070*
C7	0.6184 (3)	−0.4608 (2)	−0.1591 (2)	0.0540 (7)
H7A	0.6097	−0.5248	−0.1392	0.065*
C8	0.6181 (3)	−0.37789 (19)	−0.1068 (2)	0.0444 (6)
H8A	0.6053	−0.3865	−0.0525	0.053*
C9	0.6815 (2)	−0.16746 (17)	−0.22479 (17)	0.0332 (5)
C10	0.6534 (2)	−0.27237 (17)	−0.20994 (17)	0.0337 (5)
C11	0.8922 (2)	0.08967 (16)	0.20040 (15)	0.0278 (4)
C12	0.8946 (2)	−0.01519 (16)	0.20175 (15)	0.0281 (4)
C13	0.9639 (2)	−0.06631 (17)	0.29523 (16)	0.0346 (5)
H13A	0.9681	−0.1360	0.2959	0.042*
C14	1.0260 (2)	−0.0142 (2)	0.38647 (16)	0.0405 (5)
H14A	1.0703	−0.0486	0.4484	0.049*
C15	1.0221 (2)	0.0895 (2)	0.38529 (17)	0.0419 (6)
H15A	1.0636	0.1249	0.4466	0.050*
C16	0.9568 (2)	0.14064 (17)	0.29350 (18)	0.0365 (5)
H16A	0.9559	0.2104	0.2937	0.044*
C17	0.8383 (2)	0.14901 (14)	0.10351 (17)	0.0282 (4)
C18	0.7102 (2)	0.19898 (15)	0.04996 (16)	0.0292 (4)
C19	0.6773 (2)	0.25507 (18)	−0.03716 (18)	0.0369 (5)
H19A	0.5920	0.2890	−0.0727	0.044*
C20	0.7682 (3)	0.26123 (18)	−0.07140 (19)	0.0412 (5)
H20A	0.7446	0.2991	−0.1290	0.049*
C21	0.8951 (2)	0.21017 (18)	−0.01881 (19)	0.0400 (5)
H21A	0.9573	0.2131	−0.0412	0.048*
C22	0.9287 (3)	0.15476 (17)	0.06719 (19)	0.0366 (5)
H22A	1.0137	0.1204	0.1018	0.044*
C23	0.8187 (2)	−0.07766 (15)	0.10614 (16)	0.0300 (4)
C24	0.5999 (2)	0.18908 (16)	0.07706 (17)	0.0309 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03431 (18)	0.02951 (18)	0.02666 (17)	−0.00125 (10)	0.01828 (13)	−0.00287 (9)
O1	0.0386 (8)	0.0330 (8)	0.0287 (8)	0.0015 (7)	0.0138 (7)	−0.0053 (6)
O2	0.0586 (12)	0.0359 (10)	0.0433 (10)	0.0155 (8)	0.0128 (9)	−0.0077 (7)
O3	0.0446 (10)	0.0630 (12)	0.0467 (11)	0.0160 (8)	0.0313 (9)	0.0260 (8)
O4	0.0328 (8)	0.0494 (10)	0.0328 (8)	0.0021 (7)	0.0193 (7)	0.0047 (7)
N1	0.0321 (9)	0.0371 (10)	0.0286 (9)	−0.0026 (8)	0.0174 (8)	−0.0026 (8)
N2	0.0323 (9)	0.0339 (10)	0.0325 (9)	0.0008 (8)	0.0168 (8)	−0.0031 (8)
C1	0.0441 (13)	0.0396 (13)	0.0410 (13)	−0.0049 (11)	0.0247 (11)	0.0004 (10)
C2	0.0523 (15)	0.0506 (16)	0.0521 (16)	−0.0115 (13)	0.0304 (13)	0.0044 (12)
C3	0.0485 (15)	0.075 (2)	0.0423 (14)	−0.0104 (14)	0.0288 (12)	0.0046 (13)
C4	0.0412 (13)	0.0684 (17)	0.0339 (12)	−0.0086 (12)	0.0233 (11)	−0.0095 (12)
C5	0.0477 (15)	0.0549 (17)	0.0515 (16)	−0.0021 (12)	0.0317 (13)	−0.0170 (12)
C6	0.0578 (17)	0.0476 (16)	0.074 (2)	−0.0064 (13)	0.0380 (16)	−0.0293 (15)
C7	0.0522 (16)	0.0322 (13)	0.076 (2)	−0.0053 (12)	0.0327 (15)	−0.0113 (12)
C8	0.0475 (14)	0.0354 (13)	0.0500 (15)	−0.0028 (11)	0.0259 (12)	−0.0028 (11)
C9	0.0253 (10)	0.0467 (13)	0.0273 (11)	−0.0003 (9)	0.0138 (9)	−0.0040 (9)
C10	0.0268 (10)	0.0414 (13)	0.0313 (11)	−0.0001 (9)	0.0144 (9)	−0.0076 (9)
C11	0.0261 (9)	0.0282 (10)	0.0298 (10)	0.0002 (8)	0.0154 (8)	−0.0003 (8)
C12	0.0282 (10)	0.0304 (11)	0.0269 (10)	0.0008 (8)	0.0154 (8)	0.0001 (8)
C13	0.0383 (12)	0.0330 (11)	0.0337 (11)	0.0039 (9)	0.0199 (10)	0.0056 (9)
C14	0.0416 (13)	0.0515 (14)	0.0261 (11)	0.0053 (11)	0.0166 (10)	0.0062 (10)
C15	0.0418 (12)	0.0521 (15)	0.0258 (11)	0.0020 (11)	0.0139 (10)	−0.0096 (10)
C16	0.0386 (12)	0.0322 (11)	0.0365 (12)	0.0003 (9)	0.0184 (10)	−0.0055 (9)
C17	0.0328 (11)	0.0243 (10)	0.0302 (11)	−0.0037 (8)	0.0186 (9)	−0.0015 (8)
C18	0.0345 (11)	0.0242 (10)	0.0320 (11)	−0.0024 (9)	0.0198 (9)	0.0004 (8)
C19	0.0403 (12)	0.0332 (12)	0.0382 (12)	0.0040 (10)	0.0215 (10)	0.0099 (10)
C20	0.0530 (14)	0.0362 (12)	0.0422 (13)	−0.0049 (11)	0.0305 (11)	0.0083 (10)
C21	0.0462 (13)	0.0398 (13)	0.0487 (14)	−0.0066 (11)	0.0352 (12)	0.0014 (11)
C22	0.0339 (12)	0.0389 (13)	0.0394 (13)	−0.0010 (9)	0.0211 (10)	0.0007 (9)
C23	0.0357 (11)	0.0280 (11)	0.0294 (10)	−0.0010 (9)	0.0194 (9)	−0.0010 (8)
C24	0.0346 (11)	0.0257 (10)	0.0360 (11)	0.0013 (9)	0.0211 (9)	0.0030 (9)

Geometric parameters (Å, º) top

Cu1—O1	1.9640 (15)	C6—H6A	0.9300
Cu1—O4ⁱ	1.9725 (16)	C7—C8	1.370 (4)
Cu1—N2	1.9814 (19)	C7—H7A	0.9300
Cu1—N1	1.9897 (19)	C8—H8A	0.9300
Cu1—O2	2.434 (2)	C9—C10	1.479 (3)
Cu1—C23	2.519 (2)	C11—C16	1.394 (3)
Cu1—O3ⁱ	2.557 (2)	C11—C12	1.399 (3)
Cu1—C24ⁱ	2.580 (2)	C11—C17	1.505 (3)
O1—C23	1.273 (2)	C12—C13	1.399 (3)
O2—C23	1.233 (3)	C12—C23	1.503 (3)
O3—C24	1.225 (3)	C13—C14	1.381 (3)
O3—Cu1ⁱ	2.5567 (19)	C13—H13A	0.9300
O4—C24	1.280 (3)	C14—C15	1.383 (4)
O4—Cu1ⁱ	1.9725 (16)	C14—H14A	0.9300
N1—C1	1.342 (3)	C15—C16	1.380 (3)
N1—C9	1.350 (3)	C15—H15A	0.9300
N2—C8	1.331 (3)	C16—H16A	0.9300
N2—C10	1.351 (3)	C17—C18	1.390 (3)
C1—C2	1.377 (3)	C17—C22	1.399 (3)
C1—H1A	0.9300	C18—C19	1.405 (3)
C2—C3	1.372 (4)	C18—C24	1.509 (3)
C2—H2A	0.9300	C19—C20	1.379 (3)
C3—C4	1.385 (4)	C19—H19A	0.9300
C3—H3A	0.9300	C20—C21	1.387 (3)
C4—C9	1.377 (3)	C20—H20A	0.9300
C4—H4A	0.9300	C21—C22	1.384 (3)
C5—C6	1.365 (4)	C21—H21A	0.9300
C5—C10	1.383 (3)	C22—H22A	0.9300
C5—H5A	0.9300	C24—Cu1ⁱ	2.580 (2)
C6—C7	1.378 (5)

O1—Cu1—O4ⁱ	93.92 (7)	C6—C7—H7A	120.8
O1—Cu1—N2	162.77 (7)	N2—C8—C7	122.5 (3)
O4ⁱ—Cu1—N2	95.38 (8)	N2—C8—H8A	118.8
O1—Cu1—N1	94.56 (7)	C7—C8—H8A	118.8
O4ⁱ—Cu1—N1	160.15 (7)	N1—C9—C4	121.3 (2)
N2—Cu1—N1	81.35 (8)	N1—C9—C10	114.4 (2)
O1—Cu1—O2	58.55 (6)	C4—C9—C10	124.3 (2)
O4ⁱ—Cu1—O2	96.94 (8)	N2—C10—C5	121.0 (2)
N2—Cu1—O2	105.83 (7)	N2—C10—C9	114.12 (19)
N1—Cu1—O2	102.80 (8)	C5—C10—C9	124.9 (2)
O1—Cu1—C23	29.83 (6)	C16—C11—C12	118.49 (19)
O4ⁱ—Cu1—C23	95.07 (7)	C16—C11—C17	118.75 (19)
N2—Cu1—C23	134.42 (7)	C12—C11—C17	122.34 (18)
N1—Cu1—C23	101.19 (7)	C11—C12—C13	119.90 (19)
O2—Cu1—C23	28.76 (6)	C11—C12—C23	122.91 (18)
O1—Cu1—O3ⁱ	106.45 (7)	C13—C12—C23	117.11 (19)
O4ⁱ—Cu1—O3ⁱ	56.28 (6)	C14—C13—C12	120.5 (2)
N2—Cu1—O3ⁱ	90.78 (7)	C14—C13—H13A	119.7
N1—Cu1—O3ⁱ	104.04 (7)	C12—C13—H13A	119.7
O2—Cu1—O3ⁱ	150.22 (7)	C13—C14—C15	119.7 (2)
C23—Cu1—O3ⁱ	130.98 (7)	C13—C14—H14A	120.2
O1—Cu1—C24ⁱ	99.04 (7)	C15—C14—H14A	120.2
O4ⁱ—Cu1—C24ⁱ	28.92 (6)	C16—C15—C14	120.2 (2)
N2—Cu1—C24ⁱ	96.11 (7)	C16—C15—H15A	119.9
N1—Cu1—C24ⁱ	131.58 (7)	C14—C15—H15A	119.9
O2—Cu1—C24ⁱ	123.91 (8)	C15—C16—C11	121.2 (2)
C23—Cu1—C24ⁱ	113.37 (7)	C15—C16—H16A	119.4
O3ⁱ—Cu1—C24ⁱ	27.59 (6)	C11—C16—H16A	119.4
C23—O1—Cu1	100.02 (13)	C18—C17—C22	118.57 (19)
C23—O2—Cu1	79.48 (13)	C18—C17—C11	125.76 (19)
C24—O3—Cu1ⁱ	77.28 (13)	C22—C17—C11	115.66 (19)
C24—O4—Cu1ⁱ	102.92 (13)	C17—C18—C19	119.05 (19)
C1—N1—C9	119.4 (2)	C17—C18—C24	122.42 (19)
C1—N1—Cu1	125.93 (16)	C19—C18—C24	118.37 (19)
C9—N1—Cu1	114.61 (15)	C20—C19—C18	121.8 (2)
C8—N2—C10	119.0 (2)	C20—C19—H19A	119.1
C8—N2—Cu1	125.93 (17)	C18—C19—H19A	119.1
C10—N2—Cu1	115.06 (15)	C19—C20—C21	119.1 (2)
N1—C1—C2	121.8 (2)	C19—C20—H20A	120.4
N1—C1—H1A	119.1	C21—C20—H20A	120.4
C2—C1—H1A	119.1	C22—C21—C20	119.6 (2)
C3—C2—C1	119.0 (3)	C22—C21—H21A	120.2
C3—C2—H2A	120.5	C20—C21—H21A	120.2
C1—C2—H2A	120.5	C21—C22—C17	121.9 (2)
C2—C3—C4	119.5 (2)	C21—C22—H22A	119.1
C2—C3—H3A	120.2	C17—C22—H22A	119.1
C4—C3—H3A	120.2	O2—C23—O1	121.8 (2)
C9—C4—C3	119.0 (2)	O2—C23—C12	120.6 (2)
C9—C4—H4A	120.5	O1—C23—C12	117.53 (18)
C3—C4—H4A	120.5	O2—C23—Cu1	71.76 (13)
C6—C5—C10	119.1 (3)	O1—C23—Cu1	50.14 (10)
C6—C5—H5A	120.4	C12—C23—Cu1	165.85 (15)
C10—C5—H5A	120.4	O3—C24—O4	122.5 (2)
C5—C6—C7	119.8 (2)	O3—C24—C18	121.2 (2)
C5—C6—H6A	120.1	O4—C24—C18	116.28 (18)
C7—C6—H6A	120.1	O3—C24—Cu1ⁱ	75.13 (13)
C8—C7—C6	118.5 (3)	O4—C24—Cu1ⁱ	48.16 (10)
C8—C7—H7A	120.8	C18—C24—Cu1ⁱ	161.10 (15)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1	0.93	2.58	3.081 (3)	114
C4—H4A···O4ⁱⁱ	0.93	2.59	3.378 (3)	143
C5—H5A···O4ⁱⁱ	0.93	2.51	3.304 (4)	144
C6—H6A···O3ⁱⁱⁱ	0.93	2.25	3.162 (3)	166
C16—H16A···O2^iv	0.93	2.48	3.192 (3)	133
C19—H19A···O4	0.93	2.45	2.761 (3)	100

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

Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₄H₈O₄)₂(C₁₀H₈N₂)₂]
M_r	1839.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.234 (2), 13.336 (3), 15.431 (6)
β (°)	122.16 (2)
V (Å³)	1957.1 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.15
Crystal size (mm)	0.40 × 0.26 × 0.23

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.708, 0.771
No. of measured, independent and observed [I > 2σ(I)] reflections	18687, 4472, 3708
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.118, 1.04
No. of reflections	4472
No. of parameters	280
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.60

Computer programs: SMART (Siemens, 1994), SAINT (Siemens, 1994), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—O1	1.9640 (15)	Cu1—O2	2.434 (2)
Cu1—O4ⁱ	1.9725 (16)	Cu1—C23	2.519 (2)
Cu1—N2	1.9814 (19)	Cu1—O3ⁱ	2.557 (2)
Cu1—N1	1.9897 (19)

O1—Cu1—O4ⁱ	93.92 (7)	O1—Cu1—N1	94.56 (7)
O1—Cu1—N2	162.77 (7)	O4ⁱ—Cu1—N1	160.15 (7)
O4ⁱ—Cu1—N2	95.38 (8)	N2—Cu1—N1	81.35 (8)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1	0.93	2.58	3.081 (3)	114.4
C4—H4A···O4ⁱⁱ	0.93	2.59	3.378 (3)	142.8
C5—H5A···O4ⁱⁱ	0.93	2.51	3.304 (4)	143.5
C6—H6A···O3ⁱⁱⁱ	0.93	2.25	3.162 (3)	166.0
C16—H16A···O2^iv	0.93	2.48	3.192 (3)	133.4
C19—H19A···O4	0.93	2.45	2.761 (3)	99.7

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

Acknowledgements

This work was supported by a Project of Fujian Science and Technology Committee (grant No. 2006F5067), the Natural Science Foundation of Fujian Province (grant Nos. 2008J0172 and 2008J0237) and a Student Innovation Project of Zhangzhou Normal University (grant No. 08xscxxsyxm25).

References

Bu, X. H., Tong, M. L., Chang, H. C., Kitagawa, S. & Batten, S. R. (2004). Angew. Chem. Int. Ed. 43, 192–195. Web of Science CSD CrossRef CAS Google Scholar
He, H.-Y., Zhou, Y.-L. & Gao, J. (2007). Acta Cryst. E63, m2007. Web of Science CSD CrossRef IUCr Journals Google Scholar
He, H.-Y. & Zhu, L.-G. (2003). Acta Cryst. E59, o174–o176. Web of Science CSD CrossRef IUCr Journals Google Scholar
Huang, X. C., Zhang, J. P., Lin, Y. Y., Yu, X. L. & Chen, X. M. (2004). Chem. Commun. pp. 1100–1101. Web of Science CSD CrossRef Google Scholar
Long, L. S., Chen, X. M., Tong, M. L., Sun, Z. G., Ren, Y. P., Huang, R. B. & Zheng, L. S. (2001). J. Chem. Soc. Dalton Trans. pp. 2888–2890. Web of Science CSD CrossRef Google Scholar
Ma, B. Q., Sun, H. L. & Gao, S. (2003). Chem. Commun. pp. 2164–2165. Web of Science CSD CrossRef Google Scholar
Rao, C. N. R., Natarajan, S. & Vaidhyanathan, R. (2004). Angew. Chem. Int. Ed. 43, 1466–1496. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1994). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Yaghi, O. M., O'Keeffe, M., Ockwig, N. W., Chae, H. K., Eddaoudi, M. & Kim, J. (2003). Nature (London), 423, 705–714. Web of Science CrossRef PubMed CAS Google Scholar
Yang, S. Y., Long, L. S., Jiang, Y. B., Huang, R. B. & Zheng, L. S. (2002). Chem. Mater. 14, 3229–3230. Web of Science CSD CrossRef CAS Google Scholar
Zhang, J. P., Zheng, S. L., Huang, X. C. & Chen, X. M. (2004). Angew. Chem. Int. Ed. 43, 206–209. Web of Science CSD CrossRef CAS Google Scholar
Zhu, H. L., Tong, Y. X. & Chen, X. M. (2001). Transition Met. Chem. 26, 528–531. Web of Science CSD CrossRef CAS Google Scholar