catena-Poly[[(1,10-phenanthroline-κ2N,N′)copper(II)]-μ-2,2′-iminodibenzoato-κ4O,O′:O′′,O′′′]

Yuste-Vivas, C.; Coutinho, J.T.; Pereira, L.C.J.; Silva, M.R.

doi:10.1107/S1600536813009203

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Pages m255-m256

https://doi.org/10.1107/S1600536813009203

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catena-Poly[[(1,10-phenanthroline-κ²N,N′)copper(II)]-μ-2,2′-iminodibenzoato-κ⁴O,O′:O′′,O′′′]

Consuelo Yuste-Vivas,^a ^* Joana T. Coutinho,^b Laura C. J. Pereira ^b and Manuela Ramos Silva ^a

^aCEMDRX, Physics Department, University of Coimbra, P-3004-516 Coimbra, Portugal, and ^bSolid State Group UCQR, IST/ITN, Universidade Técnica de Lisboa, Estrada Nacional 10, 2686-953 Sacavém, Portugal
^*Correspondence e-mail: xelo@teor.fis.uc.pt

(Received 15 February 2013; accepted 4 April 2013; online 13 April 2013)

The structure of the title compound, [Cu(C₁₄H₉NO₄)(C₁₂H₈N₂)]_n, consists of zigzag polymeric chains along the c axis. The asymmetric unit contains one Cu^II atom which is coordinated by one 2,2′-iminodibenzoate ligand and a one phenanthroline unit. Two intramolecular N—H⋯O hydrogen bonds occur. The supramolecular structure is characterized by weak C—H⋯O hydrogen bonds and π–π stacking interactions, forming a three-dimensional supramolecular network. The shortest centroid–centroid distances between neighbouring phenanthroline aromatic rings and 2,2′-iminodibenzoate rings are 3.684 (1) and 3.640 Å, respectively. The shortest intrachain Cu⋯Cu distance is 7.2885 (9) and the shortest Cu⋯Cu distance between Cu atoms in different chains is 7.1103 (6) Å.

Related literature

For general background to Cu^II low-dimensional polynuclear magnetic materials, see: Fabelo et al. (2009 ); Martins et al. (2008a ,b ); Silva et al. (2001 ); Yuste et al. (2007 , 2008 ). For structural and coordination information for 2,2′-iminodibenzoic acid, see: Field & Venkataraman (2002 ); Gao et al. (2009 ); Lin et al. (2006 ).

Experimental

Crystal data

[Cu(C₁₄H₉NO₄)(C₁₂H₈N₂)]
M_r = 498.98
Monoclinic, C 2/c
a = 31.7536 (6) Å
b = 9.8492 (2) Å
c = 14.4865 (3) Å
β = 113.222 (1)°
V = 4163.56 (14) Å³
Z = 8
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 293 K
0.1 × 0.08 × 0.07 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.898, T_max = 0.971
36778 measured reflections
3976 independent reflections
2900 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.089
S = 1.02
3976 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	2.07	2.708 (5)	131
N1—H1⋯O3	0.86	2.06	2.701 (5)	130
C17—H17⋯O2ⁱ	0.93	2.55	3.308 (4)	139
C23—H23⋯O3ⁱⁱ	0.93	2.38	3.185 (4)	145
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813009203/bt6890sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813009203/bt6890Isup2.hkl

checkCIF report

Comment top

This work is part of a project of synthesizing low dimensional polynuclear magnetic materials with Copper(II) and oxygen-donors bridging ligands (Fabelo et al., 2009; Martins et al., 2008a; Martins et al., 2008b; Silva et al., 2001; Yuste et al., 2007, 2008).

The target of this work is the use of an aromatic dicarboxylic acid, such as the 2,2'-iminodibenzoic acid, (H₂IDC) and another quelate, known as ''coligand'' that will block some coordination positions of the Copper(II) metal ion, modulating the dimensionality of the resulting compound. (Gao et al., 2009; Lin et al., 2006; Yuste et al., 2008).

The structure of this compound consists of neutral chains of formula [Cu(C₁₄H₉NO₄)(C₁₂H₈N₂)]_n, growing along the c-axis, in a zigzag mode, where the 2,2'-iminodibenzoate (IDC^2-) units act as linkers between two Cu(II) ions, in a bis-bidentate mode, and the phenanthroline molecules are placed out-of-chain. The whole compound adopts a three dimensional supramolecular structure by weak π-π stacking. The shortest intra- and interchain copper···copper distances are 7.2885 (9) Å [Cu1···Cu1ⁱ; (i) = x, 1 - y, -1/2 + z] and 7.1103 (6) Å [Cu1···Cu1^v; (v) = 1/2 - x, 1/2 - y, 1 - z], respectively.

The Copper(II) ion shows a distorted octahedral environment, CuN₂O₄, due to the Jahn-Teller effect. The equatorial positions are occupied by the two nitrogen atoms from the phenanthroline ligand, [N1 and N2], and two oxygen atoms [O1 and O4], from two different carboxylate units of the IDC^2- ligand, varying the distances in a very narrow range of [1.940–2.026 Å]. Another two oxygen atoms [O2 and O3], with bond length values 2.618 (2) and 2.438 (3) Å respectively, are placed in the axial positions. The 2,2'-iminodibenzoate links two neighboring Copper(II) metal ions, being the bite angle 55.19 (11)° [O1—Cu1—O2] and 58.92 (11)° [O3—Cu1ⁱⁱ—O4]. [(ii) = x, -y, -1/2 + z]. The ligand is not planar, with a maximum deviation of 1.472 (5) Å for C10 from the mean plane, being the dihedral angle between the two aromatic rings 52.25 (3)°, which is greater than those already reported (Field et al., 2002; Gao et al., 2009).

Intramolecular hydrogen bond interactions exist inside the 2,2'-iminodibenzoate unit between the nitrogen atom [N1] from the amino group and two oxygen atoms [O2 and O3] from the carboxylate groups. The intermolecular π-π stacking interaction exists in between two aromatic rings of two neighbor phenantrolines and also between the aromatic rings of two neighbor 2,2'-iminodibenzoate moieties. These weak π-π interactions, stabilize the crystal structure of the complex. The shortest distances 'centroid-to-centroid' between neighbor aromatic ring of two phenantrolines and two neighbor 2,2'-iminodibenzoate are 3.684 (1) and 3.640 Å respectively.

Related literature top

For general background to Cu^II low-dimensional polynuclear magnetic materials, see: Fabelo et al. (2009); Martins et al. (2008a,b); Silva et al. (2001); Yuste et al. (2007, 2008). For structural and coordination information for 2,2'-iminodibenzoic acid, see: Field & Venkataraman (2002); Gao et al. (2009); Lin et al. (2006).

Experimental top

All the reagents, phenanthroline, 2,2'-Iminodibenzoic acid, and the metallic salt Cu(NO₃)₂.3H₂O, were purchased from commercial sources and used as received with no further purifications.

An aqueous solution containing Cu(NO₃)₂.3H₂O (1 mmol, 0.0242 g), Iminodibenzoic acid (1 mmol, 0.0257 g) and phenanthroline, ((2 mmol, 0.0361 g), was stirred during 30 minutes and placed in a 25 mL Teflon-lined autoclave and then heated at 120°C during 48 h. Dark green crystals were obtained by filtration, washed with water and dried in air. Ca. 36% yield based on Cu.

Structure description top

For general background to Cu^II low-dimensional polynuclear magnetic materials, see: Fabelo et al. (2009); Martins et al. (2008a,b); Silva et al. (2001); Yuste et al. (2007, 2008). For structural and coordination information for 2,2'-iminodibenzoic acid, see: Field & Venkataraman (2002); Gao et al. (2009); Lin et al. (2006).

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).

Figures top

	Fig. 1. : The molecular structure of the title compound, showing the atom-labelling scheme and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) x, 1 - y, 1/2 - z; (ii) x, 1 - y, 1/2 + z.]
	Fig. 2. : View of the crystal packing of the title compound, projected along c.
	Fig. 3. : A view showing part of the three-dimensional supramolecular network linked by weak π-π stacking interactions (yellow dotted lines).

catena-Poly[[(1,10-phenanthroline-κ²N,N')copper(II)]-µ-2,2'-iminodibenzoato-κ⁴O,O':O'',O'''] top

Crystal data top

[Cu(C₁₄H₉NO₄)(C₁₂H₈N₂)]	F(000) = 2040
M_r = 498.98	D_x = 1.592 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6606 reflections
a = 31.7536 (6) Å	θ = 2.2–20.8°
b = 9.8492 (2) Å	µ = 1.09 mm⁻¹
c = 14.4865 (3) Å	T = 293 K
β = 113.222 (1)°	Blocks, green
V = 4163.56 (14) Å³	0.1 × 0.08 × 0.07 mm
Z = 8

Data collection top

Bruker APEXII CCD area-detector diffractometer	3976 independent reflections
Radiation source: fine-focus sealed tube	2900 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
φ and ω scans	θ_max = 25.8°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −38→38
T_min = 0.898, T_max = 0.971	k = −12→12
36778 measured reflections	l = −17→17

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.037P)² + 5.032P] where P = (F_o² + 2F_c²)/3
3976 reflections	(Δ/σ)_max < 0.001
307 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Cu(C₁₄H₉NO₄)(C₁₂H₈N₂)]	V = 4163.56 (14) Å³
M_r = 498.98	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 31.7536 (6) Å	µ = 1.09 mm⁻¹
b = 9.8492 (2) Å	T = 293 K
c = 14.4865 (3) Å	0.1 × 0.08 × 0.07 mm
β = 113.222 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3976 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2900 reflections with I > 2σ(I)
T_min = 0.898, T_max = 0.971	R_int = 0.061
36778 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.02	Δρ_max = 0.29 e Å⁻³
3976 reflections	Δρ_min = −0.40 e Å⁻³
307 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	0.172485 (11)	0.45882 (4)	0.30778 (3)	0.03710 (12)
N1	0.07823 (8)	0.7287 (3)	0.46195 (18)	0.0466 (6)
H1	0.1021	0.6781	0.4882	0.056*
N2	0.20508 (7)	0.2788 (2)	0.35164 (16)	0.0361 (5)
N3	0.23714 (7)	0.5223 (2)	0.34707 (17)	0.0370 (5)
O4	0.11136 (6)	0.6223 (2)	0.75794 (15)	0.0448 (5)
O1	0.14757 (7)	0.6413 (2)	0.27927 (16)	0.0479 (5)
O2	0.14659 (7)	0.6025 (2)	0.42821 (15)	0.0495 (5)
O3	0.13160 (6)	0.5939 (2)	0.63028 (15)	0.0441 (5)
C1	0.13485 (9)	0.6710 (3)	0.3501 (2)	0.0387 (7)
C2	0.10555 (8)	0.7946 (3)	0.3344 (2)	0.0361 (7)
C3	0.10490 (9)	0.8884 (3)	0.2622 (2)	0.0444 (7)
H3	0.1217	0.8703	0.2237	0.053*
C4	0.08029 (11)	1.0071 (3)	0.2458 (3)	0.0539 (9)
H4	0.0798	1.0670	0.1957	0.065*
C5	0.05662 (10)	1.0354 (3)	0.3043 (3)	0.0560 (9)
H5	0.0414	1.1179	0.2967	0.067*
C6	0.05500 (10)	0.9437 (3)	0.3744 (3)	0.0528 (8)
H6	0.0379	0.9641	0.4120	0.063*
C7	0.07871 (9)	0.8197 (3)	0.3902 (2)	0.0384 (7)
C8	0.04358 (9)	0.7090 (3)	0.4972 (2)	0.0414 (7)
C9	−0.00235 (10)	0.7313 (4)	0.4351 (3)	0.0537 (9)
H9	−0.0099	0.7659	0.3708	0.064*
C10	−0.03645 (10)	0.7024 (4)	0.4680 (3)	0.0603 (10)
H10	−0.0669	0.7152	0.4249	0.072*
C11	−0.02635 (10)	0.6550 (4)	0.5636 (3)	0.0605 (10)
H11	−0.0497	0.6372	0.5855	0.073*
C12	0.01899 (10)	0.6343 (3)	0.6269 (3)	0.0492 (8)
H12	0.0262	0.6032	0.6919	0.059*
C13	0.05402 (9)	0.6595 (3)	0.5942 (2)	0.0383 (7)
C14	0.10206 (9)	0.6238 (3)	0.6641 (2)	0.0381 (7)
C15	0.18760 (10)	0.1574 (3)	0.3531 (2)	0.0440 (7)
H15	0.1561	0.1494	0.3341	0.053*
C16	0.21466 (11)	0.0407 (3)	0.3820 (2)	0.0502 (8)
H16	0.2012	−0.0432	0.3822	0.060*
C17	0.26097 (11)	0.0504 (3)	0.4102 (2)	0.0500 (8)
H17	0.2793	−0.0266	0.4299	0.060*
C18	0.28067 (10)	0.1772 (3)	0.4090 (2)	0.0421 (7)
C19	0.32883 (10)	0.2002 (4)	0.4383 (2)	0.0519 (8)
H19	0.3491	0.1273	0.4580	0.062*
C20	0.34496 (10)	0.3263 (4)	0.4376 (2)	0.0515 (8)
H20	0.3764	0.3388	0.4582	0.062*
C21	0.31555 (9)	0.4409 (3)	0.4063 (2)	0.0409 (7)
C22	0.32977 (11)	0.5755 (4)	0.4042 (2)	0.0516 (9)
H22	0.3607	0.5948	0.4229	0.062*
C23	0.29850 (11)	0.6773 (3)	0.3750 (2)	0.0523 (8)
H23	0.3080	0.7664	0.3737	0.063*
C24	0.25214 (10)	0.6482 (3)	0.3469 (2)	0.0454 (7)
H24	0.2311	0.7190	0.3274	0.055*
C25	0.26837 (9)	0.4207 (3)	0.3767 (2)	0.0357 (6)
C26	0.25100 (9)	0.2879 (3)	0.3789 (2)	0.0351 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03325 (18)	0.0380 (2)	0.0386 (2)	0.00164 (16)	0.01251 (14)	−0.00015 (17)
N1	0.0341 (13)	0.0582 (17)	0.0465 (16)	0.0182 (12)	0.0148 (11)	0.0099 (13)
N2	0.0334 (12)	0.0379 (14)	0.0331 (13)	−0.0015 (10)	0.0091 (10)	−0.0031 (11)
N3	0.0373 (12)	0.0364 (14)	0.0364 (13)	−0.0009 (11)	0.0137 (10)	−0.0022 (11)
O4	0.0373 (10)	0.0534 (13)	0.0395 (12)	0.0011 (10)	0.0106 (9)	−0.0050 (10)
O1	0.0541 (12)	0.0437 (12)	0.0529 (13)	0.0095 (10)	0.0286 (11)	0.0050 (11)
O2	0.0522 (12)	0.0514 (13)	0.0428 (13)	0.0222 (10)	0.0166 (10)	0.0085 (11)
O3	0.0325 (10)	0.0517 (13)	0.0484 (13)	0.0064 (9)	0.0162 (9)	0.0097 (10)
C1	0.0311 (14)	0.0354 (16)	0.0434 (18)	0.0016 (12)	0.0081 (13)	−0.0023 (14)
C2	0.0276 (13)	0.0328 (16)	0.0384 (16)	0.0010 (11)	0.0029 (12)	−0.0023 (13)
C3	0.0379 (15)	0.0434 (18)	0.0443 (18)	−0.0045 (14)	0.0081 (13)	−0.0003 (15)
C4	0.0439 (17)	0.0402 (18)	0.063 (2)	−0.0025 (14)	0.0055 (16)	0.0098 (16)
C5	0.0418 (17)	0.0348 (18)	0.071 (2)	0.0068 (15)	−0.0001 (16)	0.0034 (18)
C6	0.0398 (16)	0.051 (2)	0.059 (2)	0.0143 (15)	0.0105 (15)	−0.0053 (17)
C7	0.0285 (14)	0.0407 (17)	0.0370 (17)	0.0064 (12)	0.0033 (12)	0.0004 (14)
C8	0.0330 (15)	0.0418 (17)	0.0445 (18)	0.0066 (13)	0.0101 (13)	−0.0051 (14)
C9	0.0355 (16)	0.067 (2)	0.052 (2)	0.0124 (15)	0.0096 (14)	−0.0008 (17)
C10	0.0299 (16)	0.072 (3)	0.069 (3)	0.0086 (16)	0.0089 (16)	−0.005 (2)
C11	0.0356 (17)	0.068 (2)	0.083 (3)	−0.0017 (16)	0.0282 (17)	−0.006 (2)
C12	0.0401 (16)	0.052 (2)	0.056 (2)	−0.0007 (15)	0.0197 (15)	−0.0052 (16)
C13	0.0289 (14)	0.0340 (16)	0.0484 (18)	0.0012 (12)	0.0113 (12)	−0.0069 (14)
C14	0.0334 (15)	0.0320 (16)	0.0460 (19)	−0.0047 (12)	0.0125 (13)	−0.0006 (14)
C15	0.0420 (16)	0.0425 (19)	0.0415 (18)	−0.0063 (14)	0.0100 (13)	−0.0033 (14)
C16	0.064 (2)	0.0330 (17)	0.0458 (18)	−0.0072 (16)	0.0138 (15)	−0.0010 (15)
C17	0.060 (2)	0.0400 (18)	0.0423 (18)	0.0115 (16)	0.0119 (15)	−0.0002 (15)
C18	0.0449 (16)	0.0439 (18)	0.0341 (17)	0.0076 (14)	0.0120 (13)	−0.0006 (14)
C19	0.0391 (17)	0.064 (2)	0.050 (2)	0.0151 (16)	0.0141 (14)	0.0007 (17)
C20	0.0322 (15)	0.073 (2)	0.050 (2)	0.0047 (16)	0.0167 (14)	−0.0047 (18)
C21	0.0343 (14)	0.056 (2)	0.0358 (16)	−0.0040 (14)	0.0170 (12)	−0.0041 (15)
C22	0.0399 (17)	0.070 (2)	0.048 (2)	−0.0164 (16)	0.0203 (14)	−0.0093 (17)
C23	0.060 (2)	0.050 (2)	0.051 (2)	−0.0174 (17)	0.0258 (16)	−0.0057 (16)
C24	0.0505 (18)	0.0392 (18)	0.0472 (19)	−0.0048 (14)	0.0200 (15)	−0.0043 (15)
C25	0.0356 (14)	0.0425 (17)	0.0295 (15)	−0.0012 (12)	0.0135 (12)	−0.0031 (12)
C26	0.0361 (14)	0.0399 (16)	0.0284 (15)	0.0021 (12)	0.0117 (12)	−0.0006 (13)

Geometric parameters (Å, º) top

Cu1—O1	1.942 (2)	C8—C13	1.397 (4)
Cu1—O4ⁱ	1.9548 (19)	C9—C10	1.375 (4)
Cu1—N3	2.002 (2)	C9—H9	0.9300
Cu1—N2	2.025 (2)	C10—C11	1.374 (5)
Cu1—O3ⁱ	2.4360 (19)	C10—H10	0.9300
Cu1—C14ⁱ	2.515 (3)	C11—C12	1.383 (4)
N1—C7	1.377 (4)	C11—H11	0.9300
N1—C8	1.398 (4)	C12—C13	1.392 (4)
N1—H1	0.8600	C12—H12	0.9300
N2—C15	1.322 (4)	C13—C14	1.503 (4)
N2—C26	1.355 (3)	C14—Cu1ⁱⁱ	2.515 (3)
N3—C24	1.329 (4)	C15—C16	1.397 (4)
N3—C25	1.354 (3)	C15—H15	0.9300
O4—C14	1.272 (3)	C16—C17	1.366 (4)
O4—Cu1ⁱⁱ	1.9548 (19)	C16—H16	0.9300
O1—C1	1.276 (3)	C17—C18	1.399 (4)
O2—C1	1.241 (3)	C17—H17	0.9300
O3—C14	1.253 (3)	C18—C26	1.393 (4)
O3—Cu1ⁱⁱ	2.4360 (19)	C18—C19	1.435 (4)
C1—C2	1.494 (4)	C19—C20	1.345 (5)
C2—C3	1.389 (4)	C19—H19	0.9300
C2—C7	1.409 (4)	C20—C21	1.421 (4)
C3—C4	1.373 (4)	C20—H20	0.9300
C3—H3	0.9300	C21—C25	1.400 (4)
C4—C5	1.366 (5)	C21—C22	1.404 (4)
C4—H4	0.9300	C22—C23	1.357 (4)
C5—C6	1.374 (5)	C22—H22	0.9300
C5—H5	0.9300	C23—C24	1.394 (4)
C6—C7	1.406 (4)	C23—H23	0.9300
C6—H6	0.9300	C24—H24	0.9300
C8—C9	1.397 (4)	C25—C26	1.425 (4)

O1—Cu1—O4ⁱ	92.16 (9)	C11—C10—C9	121.2 (3)
O1—Cu1—N3	93.31 (9)	C11—C10—H10	119.4
O4ⁱ—Cu1—N3	171.94 (9)	C9—C10—H10	119.4
O1—Cu1—N2	172.92 (9)	C10—C11—C12	119.1 (3)
O4ⁱ—Cu1—N2	93.93 (9)	C10—C11—H11	120.5
N3—Cu1—N2	81.03 (9)	C12—C11—H11	120.5
O1—Cu1—O3ⁱ	88.28 (8)	C11—C12—C13	120.7 (3)
O4ⁱ—Cu1—O3ⁱ	58.99 (7)	C11—C12—H12	119.6
N3—Cu1—O3ⁱ	115.25 (8)	C13—C12—H12	119.6
N2—Cu1—O3ⁱ	97.95 (8)	C12—C13—C8	120.0 (3)
O1—Cu1—C14ⁱ	88.22 (9)	C12—C13—C14	117.6 (3)
O4ⁱ—Cu1—C14ⁱ	29.85 (8)	C8—C13—C14	122.3 (2)
N3—Cu1—C14ⁱ	144.48 (9)	O3—C14—O4	121.4 (2)
N2—Cu1—C14ⁱ	98.86 (9)	O3—C14—C13	120.6 (3)
O3ⁱ—Cu1—C14ⁱ	29.27 (8)	O4—C14—C13	118.0 (2)
C7—N1—C8	127.7 (2)	O3—C14—Cu1ⁱⁱ	71.87 (15)
C7—N1—H1	116.1	O4—C14—Cu1ⁱⁱ	49.89 (13)
C8—N1—H1	116.1	C13—C14—Cu1ⁱⁱ	165.6 (2)
C15—N2—C26	117.7 (2)	N2—C15—C16	122.5 (3)
C15—N2—Cu1	129.13 (19)	N2—C15—H15	118.8
C26—N2—Cu1	113.09 (18)	C16—C15—H15	118.8
C24—N3—C25	118.2 (2)	C17—C16—C15	119.6 (3)
C24—N3—Cu1	128.2 (2)	C17—C16—H16	120.2
C25—N3—Cu1	113.59 (18)	C15—C16—H16	120.2
C14—O4—Cu1ⁱⁱ	100.26 (16)	C16—C17—C18	119.5 (3)
C1—O1—Cu1	105.80 (18)	C16—C17—H17	120.2
C14—O3—Cu1ⁱⁱ	78.86 (16)	C18—C17—H17	120.2
O2—C1—O1	122.2 (3)	C26—C18—C17	116.8 (3)
O2—C1—C2	121.8 (3)	C26—C18—C19	118.6 (3)
O1—C1—C2	116.0 (3)	C17—C18—C19	124.5 (3)
C3—C2—C7	118.8 (3)	C20—C19—C18	120.5 (3)
C3—C2—C1	118.7 (3)	C20—C19—H19	119.7
C7—C2—C1	122.4 (3)	C18—C19—H19	119.7
C4—C3—C2	122.4 (3)	C19—C20—C21	122.1 (3)
C4—C3—H3	118.8	C19—C20—H20	118.9
C2—C3—H3	118.8	C21—C20—H20	118.9
C5—C4—C3	118.7 (3)	C25—C21—C22	116.2 (3)
C5—C4—H4	120.6	C25—C21—C20	118.3 (3)
C3—C4—H4	120.6	C22—C21—C20	125.5 (3)
C4—C5—C6	121.0 (3)	C23—C22—C21	120.2 (3)
C4—C5—H5	119.5	C23—C22—H22	119.9
C6—C5—H5	119.5	C21—C22—H22	119.9
C5—C6—C7	121.1 (3)	C22—C23—C24	119.8 (3)
C5—C6—H6	119.4	C22—C23—H23	120.1
C7—C6—H6	119.4	C24—C23—H23	120.1
N1—C7—C6	121.6 (3)	N3—C24—C23	122.0 (3)
N1—C7—C2	120.6 (2)	N3—C24—H24	119.0
C6—C7—C2	117.8 (3)	C23—C24—H24	119.0
C9—C8—C13	118.5 (3)	N3—C25—C21	123.6 (3)
C9—C8—N1	121.0 (3)	N3—C25—C26	116.4 (2)
C13—C8—N1	120.5 (2)	C21—C25—C26	120.1 (3)
C10—C9—C8	120.6 (3)	N2—C26—C18	123.8 (3)
C10—C9—H9	119.7	N2—C26—C25	115.8 (2)
C8—C9—H9	119.7	C18—C26—C25	120.3 (2)

O1—Cu1—N2—C15	142.7 (7)	C11—C12—C13—C14	−175.1 (3)
O4ⁱ—Cu1—N2—C15	−6.5 (3)	C9—C8—C13—C12	−0.3 (4)
N3—Cu1—N2—C15	179.8 (3)	N1—C8—C13—C12	−177.0 (3)
O3ⁱ—Cu1—N2—C15	−65.8 (3)	C9—C8—C13—C14	175.9 (3)
C14ⁱ—Cu1—N2—C15	−36.2 (3)	N1—C8—C13—C14	−0.8 (4)
O1—Cu1—N2—C26	−40.2 (8)	Cu1ⁱⁱ—O3—C14—O4	6.4 (2)
O4ⁱ—Cu1—N2—C26	170.57 (18)	Cu1ⁱⁱ—O3—C14—C13	−172.1 (3)
N3—Cu1—N2—C26	−3.10 (18)	Cu1ⁱⁱ—O4—C14—O3	−7.9 (3)
O3ⁱ—Cu1—N2—C26	111.35 (18)	Cu1ⁱⁱ—O4—C14—C13	170.6 (2)
C14ⁱ—Cu1—N2—C26	140.93 (18)	C12—C13—C14—O3	152.6 (3)
O1—Cu1—N3—C24	−1.7 (3)	C8—C13—C14—O3	−23.8 (4)
O4ⁱ—Cu1—N3—C24	130.9 (6)	C12—C13—C14—O4	−26.0 (4)
N2—Cu1—N3—C24	−177.4 (3)	C8—C13—C14—O4	157.7 (3)
O3ⁱ—Cu1—N3—C24	88.0 (3)	C12—C13—C14—Cu1ⁱⁱ	4.3 (10)
C14ⁱ—Cu1—N3—C24	89.9 (3)	C8—C13—C14—Cu1ⁱⁱ	−172.1 (7)
O1—Cu1—N3—C25	178.62 (19)	C26—N2—C15—C16	0.4 (4)
O4ⁱ—Cu1—N3—C25	−48.8 (7)	Cu1—N2—C15—C16	177.4 (2)
N2—Cu1—N3—C25	2.88 (18)	N2—C15—C16—C17	0.0 (5)
O3ⁱ—Cu1—N3—C25	−91.73 (19)	C15—C16—C17—C18	−0.4 (5)
C14ⁱ—Cu1—N3—C25	−89.8 (2)	C16—C17—C18—C26	0.3 (4)
O4ⁱ—Cu1—O1—C1	77.83 (18)	C16—C17—C18—C19	179.0 (3)
N3—Cu1—O1—C1	−108.10 (18)	C26—C18—C19—C20	0.6 (5)
N2—Cu1—O1—C1	−71.5 (8)	C17—C18—C19—C20	−178.1 (3)
O3ⁱ—Cu1—O1—C1	136.70 (18)	C18—C19—C20—C21	−1.3 (5)
C14ⁱ—Cu1—O1—C1	107.42 (18)	C19—C20—C21—C25	0.8 (5)
Cu1—O1—C1—O2	13.4 (3)	C19—C20—C21—C22	179.5 (3)
Cu1—O1—C1—C2	−167.57 (18)	C25—C21—C22—C23	0.2 (4)
O2—C1—C2—C3	160.8 (3)	C20—C21—C22—C23	−178.4 (3)
O1—C1—C2—C3	−18.2 (4)	C21—C22—C23—C24	−0.1 (5)
O2—C1—C2—C7	−19.0 (4)	C25—N3—C24—C23	0.7 (4)
O1—C1—C2—C7	162.0 (3)	Cu1—N3—C24—C23	−179.0 (2)
C7—C2—C3—C4	2.3 (4)	C22—C23—C24—N3	−0.4 (5)
C1—C2—C3—C4	−177.5 (3)	C24—N3—C25—C21	−0.5 (4)
C2—C3—C4—C5	1.8 (4)	Cu1—N3—C25—C21	179.2 (2)
C3—C4—C5—C6	−3.9 (5)	C24—N3—C25—C26	178.0 (3)
C4—C5—C6—C7	1.9 (5)	Cu1—N3—C25—C26	−2.2 (3)
C8—N1—C7—C6	29.3 (5)	C22—C21—C25—N3	0.1 (4)
C8—N1—C7—C2	−154.7 (3)	C20—C21—C25—N3	178.8 (3)
C5—C6—C7—N1	178.4 (3)	C22—C21—C25—C26	−178.4 (3)
C5—C6—C7—C2	2.3 (4)	C20—C21—C25—C26	0.3 (4)
C3—C2—C7—N1	179.6 (2)	C15—N2—C26—C18	−0.5 (4)
C1—C2—C7—N1	−0.6 (4)	Cu1—N2—C26—C18	−178.0 (2)
C3—C2—C7—C6	−4.2 (4)	C15—N2—C26—C25	−179.7 (3)
C1—C2—C7—C6	175.5 (2)	Cu1—N2—C26—C25	2.8 (3)
C7—N1—C8—C9	30.5 (5)	C17—C18—C26—N2	0.2 (4)
C7—N1—C8—C13	−152.8 (3)	C19—C18—C26—N2	−178.6 (3)
C13—C8—C9—C10	−1.3 (5)	C17—C18—C26—C25	179.3 (3)
N1—C8—C9—C10	175.4 (3)	C19—C18—C26—C25	0.6 (4)
C8—C9—C10—C11	2.0 (5)	N3—C25—C26—N2	−0.4 (4)
C9—C10—C11—C12	−1.0 (5)	C21—C25—C26—N2	178.2 (2)
C10—C11—C12—C13	−0.7 (5)	N3—C25—C26—C18	−179.6 (2)
C11—C12—C13—C8	1.3 (5)	C21—C25—C26—C18	−1.0 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.07	2.708 (5)	131
N1—H1···O3	0.86	2.06	2.701 (5)	130
C17—H17···O2ⁱⁱⁱ	0.93	2.55	3.308 (4)	139
C23—H23···O3^iv	0.93	2.38	3.185 (4)	145

Symmetry codes: (iii) −x+1/2, −y+1/2, −z+1; (iv) −x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₄H₉NO₄)(C₁₂H₈N₂)]
M_r	498.98
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	31.7536 (6), 9.8492 (2), 14.4865 (3)
β (°)	113.222 (1)
V (Å³)	4163.56 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.1 × 0.08 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.898, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	36778, 3976, 2900
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.611

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.089, 1.02
No. of reflections	3976
No. of parameters	307
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.40

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), WinGX publication routines (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.07	2.708 (5)	131
N1—H1···O3	0.86	2.06	2.701 (5)	130
C17—H17···O2ⁱ	0.93	2.55	3.308 (4)	139
C23—H23···O3ⁱⁱ	0.93	2.38	3.185 (4)	145

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1/2, −y+3/2, −z+1.

Acknowledgements

This work was supported by the Fundo Europeu de Desenvolvimento Regional-QREN-Compete through projects PTDC/FIS/102284/2008 and PEst-C/FIS/UI0036/2011 – Fundação para a Ciência e Tecnologia (FCT).

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