Bis[4-amino-3,5-bis­(pyridin-2-yl)-4H-1,2,4-triazole-κ2N2,N3]bis­(benzene-1,2-dicarb­oxy­lic acid-κO)copper(II) bis­(2-carb­oxy­benzoate)

Yan, Y.; Yu, W.-J.; Chen, J.

doi:10.1107/S1600536812000128

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages m129-m130

doi:10.1107/S1600536812000128

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Bis[4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole-κ²N²,N³]bis(benzene-1,2-dicarboxylic acid-κO)copper(II) bis(2-carboxybenzoate)

Yan Yan,^a Wen-Jing Yu ^a and Jing Chen ^a ^*

^aCollege of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin 300387, People's Republic of China
^*Correspondence e-mail: hxxychj@mail.tjnu.edu.cn

(Received 25 December 2011; accepted 3 January 2012; online 11 January 2012)

In the complex cation of the title salt, [Cu(C₁₂H₁₀N₆)₂(C₈H₆O₄)₂](C₈H₅O₄)₂, the Cu^II atom, lying on an inversion center, exhibits a distorted octahedral geometry defined by four N atoms from two 4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole ligands in the equatorial plane and two axial O atoms from two benzene-1,2-dicarboxylic acid ligands. In the crystal, the complex cations and the monodeprotonated 2-carboxybenzoate anions are connected by O—H⋯O and N—H⋯O hydrogen bonds, forming a tape along [100]. Adjacent tapes are further linked into a three-dimensional arrangement via π–π stacking interactions between the triazole and benzene rings and between the pyridine and benzene rings [centroid–centroid distances = 3.6734 (14)/3.9430 (16) and 3.8221 (14) Å]. Intramolecular N—H⋯N and O—H⋯O hydrogen bonds are also observed.

Related literature

For the coordination systems of triazole derivatives, see: Chen et al. (2011 ); Li et al. (2010 ); Zhang et al. (2011 ). For the coordination systems of aromatic polycarboxylate ligands, see: Sun et al. (2004 ); Zehnder et al. (2011 ). For the coordination systems of mixed ligands, see: Du et al. (2005 , 2006 , 2007 , 2008 ); Habib et al. (2009 ).

Experimental

Crystal data

[Cu(C₁₂H₁₀N₆)₂(C₈H₆O₄)₂](C₈H₅O₄)₂
M_r = 1202.56
Monoclinic, P 2₁ /c
a = 12.1171 (7) Å
b = 15.9875 (10) Å
c = 15.7498 (7) Å
β = 121.739 (3)°
V = 2594.8 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 294 K
0.24 × 0.23 × 0.20 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.885, T_max = 0.906
13987 measured reflections
4579 independent reflections
3594 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.098
S = 1.05
4579 reflections
388 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O6	0.90	2.23	2.957 (3)	137
N5—H5B⋯N6	0.90	2.23	2.871 (3)	128
O2—H2⋯O8ⁱ	0.82	1.83	2.619 (2)	161
O3—H3⋯O5ⁱⁱ	0.82	1.77	2.579 (2)	171
O7—H7⋯O6	0.82	1.60	2.394 (2)	163
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+1.

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: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812000128/hy2503sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812000128/hy2503Isup2.hkl

checkCIF report

Comment top

Recently, the derivatives of 1,2,4-triazole have been widely used to synthesize diverse complicated complexes (Chen et al., 2011; Li et al., 2010; Zhang et al., 2011). In addition, the aromatic polycarboxylate ligands can also be regarded as excellent candidates for building coordination frameworks (Sun et al., 2004; Zehnder et al., 2011). With regard to this, the employment of mixed ligands using the derivatives of 1,2,4-triazole and polycarboxylate ligands can be effective in constructing supramolecular structures (Du et al., 2005, 2006, 2007, 2008; Habib et al., 2009). Herein, we present the title complex prepared by the reaction of copper(II) sulfate with benzene-1,2-dicarboxylic acid (H₂pa) and 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole (2-bpt) as the mixed ligands.

The molecular structure of the title complex is illustrated in Fig. 1. In the [Cu(2-bpt)₂(H₂pa)₂]²⁺ cation, the Cu^II atom, lying on an inversion center, shows a distorted octahedral coordination environment defined by four N atoms from two 2-bpt ligands and two O atoms of the carboxylic groups from two H₂pa ligands. The 2-bpt ligand coordinates to the Cu atom in a bidentate chelating coordination mode, with the trans-conformation considering the opposite disposition of two pyridyl N atoms. With regard to the H₂pa ligand, one carboxylic group adopts a monodentate coordination mode and the other is uncoordinated. As a result, there exists a monodeprotonated Hpa anion in the asymmetric unit to balance the charge of the complex cation.

As shown in Fig. 2, the [Cu(2-bpt)₂(H₂pa)₂]²⁺ cations and the Hpa anions are interconnected to a one-dimensional tape via intermolecular O3—H3···O5ⁱ and O2—H2···O8ⁱⁱ hydrogen bonds between the carboxyl groups from H₂pa and Hpa (Table 1) [symmetry codes: (i) -x, 1-y, 1-z; (ii) 1-x, 1-y, 1-z]. The amino group from 2-bpt is involved in an intermolecular N5—H5A···O6 hydrogen bond and an intramolecular N5—H5B···N6 hydrogen bond, which further reinforce the one-dimensional tape. A strong intramolecular O7—H7···O6 hydrogen bond is also observed within the Hpa anion. Furthermore, the adjacent one-dimensional arrays are further extended to afford a three-dimensional supramolecular architecture via multiple π–π stacking interactions (Fig. 3). The centroid–centroid distances and the dihedral angles are 3.6734 (14) Å and 3.38 (9)° between the triazole (N2, N3, N4, C6, C7) and benzene (C21ⁱⁱⁱ—C26ⁱⁱⁱ) rings and 3.8221 (14) Å and 21.59 (7)° between the pyridine (N1, C1–C5) and benzene (C13ⁱ–C18ⁱ) rings and 3.9430 (16) Å and 22.25 (8)° between the pyridine (N6, C8–C12) and benzene (C13^iv–C18^iv) rings, respectively [symmetry codes: (iii) x, 1/2-y, 1/2+z; (iv) x, 1/2-y, -1/2+z].

Related literature top

For the coordination systems of triazole derivatives, see: Chen et al. (2011); Li et al. (2010); Zhang et al. (2011). For the coordination systems of aromatic polycarboxylate ligands, see: Sun et al. (2004); Zehnder et al. (2011). For the coordination systems of mixed ligands, see: Du et al. (2005, 2006, 2007, 2008); Habib et al. (2009).

Experimental top

A mixture of 2-bpt (23.8 mg, 0.1 mmol), H₂pa (8.3 mg, 0.05 mmol) and CuSO₄.5H₂O (24.9 mg, 0.1 mmol) in water (10 ml) was sealed in a Teflon-lined stainless steel vessel (20 ml), which was heated to 100°C in 24 h and then gradually cooled to room temperature at a rate of 5°C h^-1. Block blue crystals suitable for X-ray analysis were obtained in 50% yield. Analysis, calculated for C₅₆H₄₂CuN₁₂O₁₆: C 55.93, H 3.52, N 13.98%; found: C 55.07, H 3.46, N 13.79%.

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: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Except for the carboxyl H atoms, all H atoms were omitted for clarity. [Symmetry code: (A) -x, 1-y, 1-z.]
	Fig. 2. A view of the one-dimensional tape connected via N—H···O and O—H···O hydrogen bonds (red dashed lines).
	Fig. 3. A view of the three-dimensional supramolecular structure constructed via aromatic stacking interactions (green dashed lines).

Bis[4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole- κ²N²,N³]bis(benzene-1,2-dicarboxylic acid-κO)copper(II) bis(2-carboxybenzoate) top

Crystal data top

[Cu(C₁₂H₁₀N₆)₂(C₈H₆O₄)₂](C₈H₅O₄)₂	F(000) = 1238
M_r = 1202.56	D_x = 1.539 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4780 reflections
a = 12.1171 (7) Å	θ = 2.2–25.4°
b = 15.9875 (10) Å	µ = 0.51 mm⁻¹
c = 15.7498 (7) Å	T = 294 K
β = 121.739 (3)°	Block, blue
V = 2594.8 (2) Å³	0.24 × 0.23 × 0.20 mm
Z = 2

Data collection top

Bruker APEX CCD diffractometer	4579 independent reflections
Radiation source: fine-focus sealed tube	3594 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→9
T_min = 0.885, T_max = 0.906	k = −18→19
13987 measured reflections	l = −18→18

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) = 0.098	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.051P)² + 0.7095P] where P = (F_o² + 2F_c²)/3
4579 reflections	(Δ/σ)_max = 0.001
388 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Cu(C₁₂H₁₀N₆)₂(C₈H₆O₄)₂](C₈H₅O₄)₂	V = 2594.8 (2) Å³
M_r = 1202.56	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.1171 (7) Å	µ = 0.51 mm⁻¹
b = 15.9875 (10) Å	T = 294 K
c = 15.7498 (7) Å	0.24 × 0.23 × 0.20 mm
β = 121.739 (3)°

Data collection top

Bruker APEX CCD diffractometer	4579 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3594 reflections with I > 2σ(I)
T_min = 0.885, T_max = 0.906	R_int = 0.023
13987 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.05	Δρ_max = 0.22 e Å⁻³
4579 reflections	Δρ_min = −0.38 e Å⁻³
388 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	0.0000	0.5000	0.5000	0.03702 (13)
O5	0.25819 (17)	0.25012 (10)	0.25335 (15)	0.0578 (5)
O6	0.42188 (18)	0.33760 (10)	0.30636 (14)	0.0557 (5)
O7	0.61160 (19)	0.35032 (10)	0.29636 (15)	0.0582 (5)
H7	0.5561	0.3418	0.3103	0.087*
O8	0.71299 (18)	0.27995 (10)	0.23886 (15)	0.0612 (5)
N1	0.11634 (16)	0.58006 (11)	0.48080 (13)	0.0357 (4)
N2	0.12225 (17)	0.41813 (11)	0.49978 (14)	0.0384 (4)
N3	0.14291 (17)	0.33373 (11)	0.51187 (14)	0.0398 (4)
N4	0.28569 (17)	0.39093 (11)	0.48400 (13)	0.0364 (4)
N5	0.38715 (19)	0.40434 (13)	0.46593 (16)	0.0509 (5)
H5A	0.3530	0.3915	0.4012	0.076*
H5B	0.4406	0.3643	0.5075	0.076*
N6	0.4013 (2)	0.22776 (13)	0.50357 (16)	0.0519 (5)
C1	0.2106 (2)	0.54244 (14)	0.47258 (16)	0.0358 (5)
C2	0.1071 (2)	0.66321 (14)	0.47397 (18)	0.0430 (5)
H2A	0.0436	0.6896	0.4805	0.052*
C3	0.1889 (2)	0.71151 (15)	0.45752 (19)	0.0500 (6)
H3A	0.1800	0.7694	0.4528	0.060*
C4	0.2829 (2)	0.67294 (15)	0.4483 (2)	0.0511 (6)
H4	0.3383	0.7044	0.4368	0.061*
C5	0.2950 (2)	0.58683 (15)	0.45617 (18)	0.0451 (6)
H5	0.3587	0.5596	0.4505	0.054*
C6	0.2094 (2)	0.45237 (13)	0.48423 (15)	0.0346 (5)
C7	0.2428 (2)	0.31780 (14)	0.50288 (16)	0.0374 (5)
C8	0.3001 (2)	0.23437 (14)	0.51511 (16)	0.0398 (5)
C9	0.4507 (3)	0.15095 (18)	0.5139 (2)	0.0652 (8)
H9	0.5203	0.1444	0.5051	0.078*
C10	0.4054 (3)	0.08162 (18)	0.5366 (2)	0.0683 (8)
H10	0.4430	0.0296	0.5426	0.082*
C11	0.3039 (3)	0.09019 (17)	0.5503 (2)	0.0629 (7)
H11	0.2719	0.0440	0.5665	0.075*
C12	0.2495 (2)	0.16788 (15)	0.53986 (18)	0.0488 (6)
H12	0.1806	0.1755	0.5492	0.059*
C21	0.4445 (2)	0.19723 (13)	0.26040 (16)	0.0360 (5)
C22	0.5573 (2)	0.20464 (13)	0.25486 (16)	0.0365 (5)
C23	0.6072 (2)	0.13201 (14)	0.23817 (19)	0.0465 (6)
H23	0.6802	0.1362	0.2332	0.056*
C24	0.5527 (3)	0.05483 (15)	0.2289 (2)	0.0536 (7)
H24	0.5893	0.0076	0.2188	0.064*
C25	0.4435 (2)	0.04748 (14)	0.2345 (2)	0.0526 (7)
H25	0.4056	−0.0046	0.2282	0.063*
C26	0.3915 (2)	0.11756 (14)	0.24943 (19)	0.0461 (6)
H26	0.3172	0.1119	0.2525	0.055*
C27	0.3693 (2)	0.26633 (14)	0.27388 (17)	0.0420 (5)
C28	0.6319 (2)	0.28304 (14)	0.26291 (18)	0.0423 (5)
O1	0.14046 (17)	0.52179 (11)	0.68003 (12)	0.0519 (4)
O2	0.15757 (19)	0.60865 (11)	0.79643 (15)	0.0611 (5)
H2	0.2051	0.6341	0.7829	0.092*
O3	−0.12352 (19)	0.62542 (11)	0.74566 (13)	0.0596 (5)
H3	−0.1594	0.6665	0.7517	0.089*
O4	−0.0100 (2)	0.62734 (12)	0.91204 (14)	0.0656 (5)
C13	0.0569 (2)	0.47914 (14)	0.78016 (16)	0.0375 (5)
C14	0.0682 (2)	0.39419 (15)	0.76748 (17)	0.0450 (6)
H14	0.1108	0.3770	0.7356	0.054*
C15	0.0174 (2)	0.33481 (15)	0.8014 (2)	0.0543 (7)
H15	0.0240	0.2782	0.7910	0.065*
C16	−0.0429 (3)	0.35987 (16)	0.8505 (2)	0.0555 (7)
H16	−0.0748	0.3201	0.8752	0.067*
C17	−0.0561 (2)	0.44334 (16)	0.86325 (18)	0.0502 (6)
H17A	−0.0970	0.4595	0.8967	0.060*
C18	−0.0091 (2)	0.50426 (14)	0.82691 (17)	0.0391 (5)
C19	0.1203 (2)	0.53840 (15)	0.74604 (17)	0.0407 (5)
C20	−0.0436 (2)	0.59263 (15)	0.83447 (18)	0.0436 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0356 (2)	0.0354 (2)	0.0541 (2)	0.00117 (16)	0.03318 (19)	0.00233 (17)
O5	0.0499 (11)	0.0419 (10)	0.0929 (13)	0.0050 (8)	0.0454 (10)	0.0014 (9)
O6	0.0716 (12)	0.0328 (9)	0.0875 (13)	−0.0053 (8)	0.0589 (11)	−0.0126 (9)
O7	0.0693 (12)	0.0329 (9)	0.0952 (14)	−0.0116 (8)	0.0589 (12)	−0.0105 (9)
O8	0.0668 (12)	0.0412 (10)	0.1046 (15)	−0.0081 (9)	0.0650 (12)	−0.0038 (9)
N1	0.0327 (10)	0.0386 (11)	0.0434 (10)	0.0011 (8)	0.0253 (9)	0.0018 (8)
N2	0.0353 (10)	0.0378 (10)	0.0512 (11)	0.0023 (8)	0.0290 (9)	0.0039 (8)
N3	0.0385 (10)	0.0367 (10)	0.0531 (11)	0.0022 (8)	0.0302 (10)	0.0019 (9)
N4	0.0326 (10)	0.0420 (11)	0.0438 (10)	0.0018 (8)	0.0266 (9)	−0.0004 (8)
N5	0.0474 (12)	0.0530 (12)	0.0759 (14)	−0.0009 (10)	0.0488 (12)	0.0003 (10)
N6	0.0527 (13)	0.0478 (12)	0.0694 (14)	0.0089 (10)	0.0420 (12)	0.0006 (10)
C1	0.0326 (12)	0.0397 (13)	0.0394 (12)	0.0002 (10)	0.0217 (10)	0.0010 (10)
C2	0.0412 (13)	0.0392 (13)	0.0590 (15)	0.0013 (10)	0.0334 (12)	0.0022 (11)
C3	0.0500 (15)	0.0397 (13)	0.0692 (16)	0.0008 (11)	0.0374 (14)	0.0058 (12)
C4	0.0476 (14)	0.0478 (15)	0.0722 (17)	−0.0042 (12)	0.0412 (14)	0.0073 (13)
C5	0.0406 (13)	0.0450 (14)	0.0670 (16)	0.0012 (11)	0.0400 (13)	0.0047 (12)
C6	0.0295 (11)	0.0416 (13)	0.0396 (12)	−0.0012 (10)	0.0228 (10)	−0.0013 (10)
C7	0.0360 (12)	0.0396 (12)	0.0419 (12)	0.0001 (10)	0.0242 (11)	−0.0011 (10)
C8	0.0376 (12)	0.0438 (13)	0.0396 (12)	0.0040 (10)	0.0215 (11)	−0.0015 (10)
C9	0.0694 (19)	0.0571 (18)	0.088 (2)	0.0191 (15)	0.0542 (18)	0.0044 (15)
C10	0.082 (2)	0.0498 (17)	0.087 (2)	0.0219 (15)	0.0544 (19)	0.0071 (15)
C11	0.079 (2)	0.0455 (15)	0.0756 (19)	0.0079 (14)	0.0483 (17)	0.0111 (13)
C12	0.0495 (15)	0.0489 (15)	0.0549 (15)	0.0031 (12)	0.0321 (13)	0.0028 (12)
C21	0.0402 (12)	0.0276 (11)	0.0426 (12)	0.0021 (9)	0.0234 (11)	0.0029 (9)
C22	0.0380 (12)	0.0288 (11)	0.0436 (12)	−0.0004 (9)	0.0221 (11)	0.0020 (9)
C23	0.0468 (14)	0.0352 (13)	0.0672 (16)	0.0046 (10)	0.0367 (13)	0.0010 (11)
C24	0.0622 (17)	0.0297 (13)	0.0766 (18)	0.0053 (11)	0.0419 (15)	−0.0036 (12)
C25	0.0564 (16)	0.0271 (13)	0.0743 (18)	−0.0044 (11)	0.0343 (14)	−0.0003 (11)
C26	0.0437 (13)	0.0352 (13)	0.0643 (15)	−0.0031 (10)	0.0319 (13)	0.0034 (11)
C27	0.0507 (15)	0.0343 (13)	0.0522 (14)	0.0052 (11)	0.0348 (13)	0.0059 (10)
C28	0.0449 (14)	0.0310 (12)	0.0563 (14)	0.0010 (10)	0.0303 (12)	0.0033 (10)
O1	0.0536 (10)	0.0640 (11)	0.0518 (10)	−0.0052 (8)	0.0372 (9)	−0.0058 (8)
O2	0.0810 (14)	0.0491 (11)	0.0853 (13)	−0.0210 (9)	0.0657 (12)	−0.0156 (10)
O3	0.0661 (12)	0.0499 (11)	0.0610 (11)	0.0186 (9)	0.0321 (10)	0.0014 (9)
O4	0.0877 (14)	0.0598 (12)	0.0613 (12)	0.0002 (10)	0.0474 (11)	−0.0125 (9)
C13	0.0330 (12)	0.0390 (12)	0.0415 (12)	−0.0002 (9)	0.0203 (10)	−0.0006 (10)
C14	0.0412 (13)	0.0446 (14)	0.0500 (14)	0.0053 (11)	0.0245 (12)	−0.0034 (11)
C15	0.0547 (16)	0.0355 (13)	0.0653 (16)	0.0005 (12)	0.0265 (14)	0.0019 (12)
C16	0.0521 (16)	0.0465 (15)	0.0695 (17)	−0.0066 (12)	0.0330 (15)	0.0106 (13)
C17	0.0472 (14)	0.0558 (16)	0.0591 (15)	−0.0019 (12)	0.0358 (13)	0.0038 (12)
C18	0.0361 (12)	0.0405 (13)	0.0437 (12)	−0.0006 (10)	0.0230 (11)	−0.0001 (10)
C19	0.0359 (12)	0.0426 (13)	0.0463 (13)	0.0021 (10)	0.0236 (11)	−0.0014 (11)
C20	0.0437 (14)	0.0451 (13)	0.0544 (15)	−0.0036 (11)	0.0343 (13)	−0.0008 (12)

Geometric parameters (Å, º) top

Cu1—N2	1.9781 (17)	C10—H10	0.9300
Cu1—N1	2.0409 (17)	C11—C12	1.375 (4)
Cu1—O1	2.4455 (17)	C11—H11	0.9300
O5—C27	1.236 (3)	C12—H12	0.9300
O6—C27	1.274 (3)	C21—C26	1.396 (3)
O7—C28	1.277 (3)	C21—C22	1.419 (3)
O7—H7	0.8200	C21—C27	1.516 (3)
O8—C28	1.226 (3)	C22—C23	1.397 (3)
N1—C2	1.334 (3)	C22—C28	1.511 (3)
N1—C1	1.356 (3)	C23—C24	1.371 (3)
N2—C6	1.322 (3)	C23—H23	0.9300
N2—N3	1.367 (3)	C24—C25	1.376 (3)
N3—C7	1.315 (3)	C24—H24	0.9300
N4—C6	1.350 (3)	C25—C26	1.365 (3)
N4—C7	1.374 (3)	C25—H25	0.9300
N4—N5	1.416 (2)	C26—H26	0.9300
N5—H5A	0.9001	O1—C19	1.216 (3)
N5—H5B	0.9014	O2—C19	1.311 (3)
N6—C8	1.334 (3)	O2—H2	0.8200
N6—C9	1.338 (3)	O3—C20	1.321 (3)
C1—C5	1.377 (3)	O3—H3	0.8200
C1—C6	1.453 (3)	O4—C20	1.201 (3)
C2—C3	1.384 (3)	C13—C14	1.390 (3)
C2—H2A	0.9300	C13—C18	1.401 (3)
C3—C4	1.369 (3)	C13—C19	1.487 (3)
C3—H3A	0.9300	C14—C15	1.382 (3)
C4—C5	1.383 (3)	C14—H14	0.9300
C4—H4	0.9300	C15—C16	1.373 (4)
C5—H5	0.9300	C15—H15	0.9300
C7—C8	1.469 (3)	C16—C17	1.371 (4)
C8—C12	1.382 (3)	C16—H16	0.9300
C9—C10	1.365 (4)	C17—C18	1.394 (3)
C9—H9	0.9300	C17—H17A	0.9300
C10—C11	1.362 (4)	C18—C20	1.496 (3)

N2—Cu1—N2ⁱ	180.0	C10—C11—H11	120.4
N2—Cu1—N1ⁱ	99.29 (7)	C12—C11—H11	120.4
N2ⁱ—Cu1—N1ⁱ	80.71 (7)	C11—C12—C8	118.2 (2)
N2—Cu1—N1	80.71 (7)	C11—C12—H12	120.9
N2ⁱ—Cu1—N1	99.29 (7)	C8—C12—H12	120.9
N1ⁱ—Cu1—N1	180.00 (8)	C26—C21—C22	117.6 (2)
N2—Cu1—O1	91.79 (7)	C26—C21—C27	114.24 (19)
N2ⁱ—Cu1—O1	88.21 (7)	C22—C21—C27	128.08 (19)
N1ⁱ—Cu1—O1	91.79 (6)	C23—C22—C21	117.9 (2)
N1—Cu1—O1	88.21 (6)	C23—C22—C28	113.98 (19)
C28—O7—H7	109.5	C21—C22—C28	128.06 (19)
C2—N1—C1	118.25 (18)	C24—C23—C22	122.4 (2)
C2—N1—Cu1	127.02 (15)	C24—C23—H23	118.8
C1—N1—Cu1	114.72 (14)	C22—C23—H23	118.8
C6—N2—N3	109.19 (17)	C23—C24—C25	119.7 (2)
C6—N2—Cu1	113.48 (14)	C23—C24—H24	120.1
N3—N2—Cu1	137.33 (14)	C25—C24—H24	120.1
C7—N3—N2	106.71 (18)	C26—C25—C24	119.2 (2)
C6—N4—C7	106.33 (17)	C26—C25—H25	120.4
C6—N4—N5	123.92 (18)	C24—C25—H25	120.4
C7—N4—N5	129.74 (18)	C25—C26—C21	123.1 (2)
N4—N5—H5A	105.3	C25—C26—H26	118.5
N4—N5—H5B	96.6	C21—C26—H26	118.5
H5A—N5—H5B	112.8	O5—C27—O6	122.6 (2)
C8—N6—C9	116.1 (2)	O5—C27—C21	117.6 (2)
N1—C1—C5	122.4 (2)	O6—C27—C21	119.8 (2)
N1—C1—C6	111.28 (18)	O8—C28—O7	121.4 (2)
C5—C1—C6	126.3 (2)	O8—C28—C22	118.8 (2)
N1—C2—C3	122.3 (2)	O7—C28—C22	119.8 (2)
N1—C2—H2A	118.9	C19—O1—Cu1	133.81 (16)
C3—C2—H2A	118.9	C19—O2—H2	109.5
C4—C3—C2	119.1 (2)	C20—O3—H3	109.5
C4—C3—H3A	120.5	C14—C13—C18	118.9 (2)
C2—C3—H3A	120.5	C14—C13—C19	117.5 (2)
C3—C4—C5	119.6 (2)	C18—C13—C19	123.6 (2)
C3—C4—H4	120.2	C15—C14—C13	121.2 (2)
C5—C4—H4	120.2	C15—C14—H14	119.4
C1—C5—C4	118.4 (2)	C13—C14—H14	119.4
C1—C5—H5	120.8	C16—C15—C14	119.6 (2)
C4—C5—H5	120.8	C16—C15—H15	120.2
N2—C6—N4	108.30 (18)	C14—C15—H15	120.2
N2—C6—C1	119.71 (18)	C17—C16—C15	120.3 (2)
N4—C6—C1	131.98 (19)	C17—C16—H16	119.9
N3—C7—N4	109.44 (19)	C15—C16—H16	119.9
N3—C7—C8	124.1 (2)	C16—C17—C18	121.0 (2)
N4—C7—C8	126.45 (19)	C16—C17—H17A	119.5
N6—C8—C12	123.6 (2)	C18—C17—H17A	119.5
N6—C8—C7	117.3 (2)	C17—C18—C13	119.0 (2)
C12—C8—C7	119.1 (2)	C17—C18—C20	115.9 (2)
N6—C9—C10	124.1 (3)	C13—C18—C20	125.0 (2)
N6—C9—H9	117.9	O1—C19—O2	123.0 (2)
C10—C9—H9	117.9	O1—C19—C13	123.0 (2)
C11—C10—C9	118.7 (3)	O2—C19—C13	114.0 (2)
C11—C10—H10	120.6	O4—C20—O3	124.1 (2)
C9—C10—H10	120.6	O4—C20—C18	123.9 (2)
C10—C11—C12	119.2 (3)	O3—C20—C18	111.8 (2)

N2—Cu1—N1—C2	−178.4 (2)	N6—C9—C10—C11	−0.3 (5)
N2ⁱ—Cu1—N1—C2	1.6 (2)	C9—C10—C11—C12	0.7 (4)
O1—Cu1—N1—C2	−86.26 (19)	C10—C11—C12—C8	0.4 (4)
N2—Cu1—N1—C1	2.92 (15)	N6—C8—C12—C11	−2.0 (4)
N2ⁱ—Cu1—N1—C1	−177.08 (15)	C7—C8—C12—C11	179.5 (2)
O1—Cu1—N1—C1	95.02 (15)	C26—C21—C22—C23	0.4 (3)
N1ⁱ—Cu1—N2—C6	177.47 (15)	C27—C21—C22—C23	−177.5 (2)
N1—Cu1—N2—C6	−2.53 (15)	C26—C21—C22—C28	179.2 (2)
O1—Cu1—N2—C6	−90.42 (15)	C27—C21—C22—C28	1.2 (4)
N1ⁱ—Cu1—N2—N3	−2.8 (2)	C21—C22—C23—C24	−1.1 (4)
N1—Cu1—N2—N3	177.2 (2)	C28—C22—C23—C24	179.9 (2)
O1—Cu1—N2—N3	89.3 (2)	C22—C23—C24—C25	1.0 (4)
C6—N2—N3—C7	−0.3 (2)	C23—C24—C25—C26	−0.1 (4)
Cu1—N2—N3—C7	179.97 (17)	C24—C25—C26—C21	−0.6 (4)
C2—N1—C1—C5	−0.9 (3)	C22—C21—C26—C25	0.4 (4)
Cu1—N1—C1—C5	177.90 (17)	C27—C21—C26—C25	178.6 (2)
C2—N1—C1—C6	178.53 (19)	C26—C21—C27—O5	−14.8 (3)
Cu1—N1—C1—C6	−2.6 (2)	C22—C21—C27—O5	163.2 (2)
C1—N1—C2—C3	0.9 (3)	C26—C21—C27—O6	164.4 (2)
Cu1—N1—C2—C3	−177.74 (18)	C22—C21—C27—O6	−17.6 (3)
N1—C2—C3—C4	−0.3 (4)	C23—C22—C28—O8	11.6 (3)
C2—C3—C4—C5	−0.4 (4)	C21—C22—C28—O8	−167.2 (2)
N1—C1—C5—C4	0.3 (4)	C23—C22—C28—O7	−166.9 (2)
C6—C1—C5—C4	−179.1 (2)	C21—C22—C28—O7	14.3 (4)
C3—C4—C5—C1	0.4 (4)	N2—Cu1—O1—C19	−148.0 (2)
N3—N2—C6—N4	1.2 (2)	N2ⁱ—Cu1—O1—C19	32.0 (2)
Cu1—N2—C6—N4	−179.01 (13)	N1ⁱ—Cu1—O1—C19	−48.7 (2)
N3—N2—C6—C1	−177.86 (18)	N1—Cu1—O1—C19	131.3 (2)
Cu1—N2—C6—C1	1.9 (2)	C18—C13—C14—C15	−0.9 (3)
C7—N4—C6—N2	−1.6 (2)	C19—C13—C14—C15	176.9 (2)
N5—N4—C6—N2	177.72 (18)	C13—C14—C15—C16	−1.5 (4)
C7—N4—C6—C1	177.3 (2)	C14—C15—C16—C17	2.0 (4)
N5—N4—C6—C1	−3.4 (4)	C15—C16—C17—C18	0.1 (4)
N1—C1—C6—N2	0.5 (3)	C16—C17—C18—C13	−2.5 (4)
C5—C1—C6—N2	179.9 (2)	C16—C17—C18—C20	172.8 (2)
N1—C1—C6—N4	−178.3 (2)	C14—C13—C18—C17	2.9 (3)
C5—C1—C6—N4	1.1 (4)	C19—C13—C18—C17	−174.8 (2)
N2—N3—C7—N4	−0.7 (2)	C14—C13—C18—C20	−172.0 (2)
N2—N3—C7—C8	177.3 (2)	C19—C13—C18—C20	10.3 (4)
C6—N4—C7—N3	1.4 (2)	Cu1—O1—C19—O2	−114.9 (2)
N5—N4—C7—N3	−177.8 (2)	Cu1—O1—C19—C13	68.1 (3)
C6—N4—C7—C8	−176.6 (2)	C14—C13—C19—O1	26.3 (3)
N5—N4—C7—C8	4.2 (4)	C18—C13—C19—O1	−155.9 (2)
C9—N6—C8—C12	2.3 (4)	C14—C13—C19—O2	−150.9 (2)
C9—N6—C8—C7	−179.2 (2)	C18—C13—C19—O2	26.9 (3)
N3—C7—C8—N6	179.9 (2)	C17—C18—C20—O4	62.5 (3)
N4—C7—C8—N6	−2.4 (3)	C13—C18—C20—O4	−122.5 (3)
N3—C7—C8—C12	−1.6 (3)	C17—C18—C20—O3	−112.5 (2)
N4—C7—C8—C12	176.1 (2)	C13—C18—C20—O3	62.5 (3)
C8—N6—C9—C10	−1.1 (4)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O6	0.90	2.23	2.957 (3)	137
N5—H5B···N6	0.90	2.23	2.871 (3)	128
O2—H2···O8ⁱⁱ	0.82	1.83	2.619 (2)	161
O3—H3···O5ⁱ	0.82	1.77	2.579 (2)	171
O7—H7···O6	0.82	1.60	2.394 (2)	163

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₁₀N₆)₂(C₈H₆O₄)₂](C₈H₅O₄)₂
M_r	1202.56
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	12.1171 (7), 15.9875 (10), 15.7498 (7)
β (°)	121.739 (3)
V (Å³)	2594.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.24 × 0.23 × 0.20

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.885, 0.906
No. of measured, independent and observed [I > 2σ(I)] reflections	13987, 4579, 3594
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.098, 1.05
No. of reflections	4579
No. of parameters	388
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.38

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O6	0.90	2.23	2.957 (3)	137.4
N5—H5B···N6	0.90	2.23	2.871 (3)	127.9
O2—H2···O8ⁱ	0.82	1.83	2.619 (2)	161.1
O3—H3···O5ⁱⁱ	0.82	1.77	2.579 (2)	171.0
O7—H7···O6	0.82	1.60	2.394 (2)	163.3

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

Acknowledgements

This work was supported financially by Tianjin Normal University (No. 52XQ1104).

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