Di-μ-adipato-κ4O1:O6-bis­{aqua­[5,6-di­phenyl-3-(pyridin-2-yl)-1,2,4-triazine-κ2N2,N3]copper(II)}

Xu, W.; Qi, J.–L.

doi:10.1107/S1600536812025676

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page m906

https://doi.org/10.1107/S1600536812025676

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Di-μ-adipato-κ⁴O¹:O⁶-bis{aqua[5,6-diphenyl-3-(pyridin-2-yl)-1,2,4-triazine-κ²N²,N³]copper(II)}

Wei Xu ^a ^* and Jin–Li Qi ^a

^aCenter of Applied Solid State Chemistry Research, Ningbo University, Ningbo 315211, People's Republic of China
^*Correspondence e-mail: xuwei@nbu.edu.cn

(Received 16 May 2012; accepted 5 June 2012; online 13 June 2012)

In the centrosymmetric binuclear title complex, [Cu₂(C₆H₈O₄)₂(C₂₀H₁₄N₄)₂(H₂O)₂] or [Cu₂(PDPT)₂(C₆H₈O₄)₂(H₂O)₂] (PDPT = 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine, the Cu atom displays a distorted square-pyramidal coordination environment with the basal plane occupied by two PDPT N atoms and two O atoms from different adipate dianions while a water molecule is located at the apical position. Of the two water H atoms, one participates in an intramolecular hydrogen bond whereas the second participates in an intermolecular hydrogen bond, which leads to the formation of a chain along [010].

Related literature

For the biological activity and applications of triazines, see: Garcia et al. (1995 ); Mashaly et al. (1999 ); Croot & Hunter (2000 ); Soudi et al. (2005 ); Kawamichi et al. (2009 ).

Experimental

Crystal data

[Cu₂(C₆H₈O₄)₂(C₂₀H₁₄N₄)₂(H₂O)₂]
M_r = 1072.08
Triclinic, $[P \overline 1]$
a = 9.4825 (19) Å
b = 10.616 (2) Å
c = 13.080 (3) Å
α = 78.96 (3)°
β = 68.76 (3)°
γ = 76.85 (3)°
V = 1186.4 (5) Å³
Z = 1
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 295 K
0.30 × 0.19 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID CCD diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.756, T_max = 0.863
11646 measured reflections
5295 independent reflections
3207 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.135
S = 1.02
5295 reflections
333 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O3ⁱ	0.83	1.92	2.721 (3)	161
O5—H5B⋯O1ⁱⁱ	0.83	2.06	2.878 (4)	167
Symmetry codes: (i) -x, -y, -z+1; (ii) -x, -y+1, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812025676/rk2363sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025676/rk2363Isup2.hkl

checkCIF report

Comment top

Research on coordination chemistry of triazine–derived ligands has progressed very rapidly during the past two decades (Kawamichi et al., 2009). The 1,2,4–triazine compounds are well–known in natural materials and show intersting biological, pharmacological and medicinal properties (Garcia et al., 1995). The 3–(2–pyridyl)–5,6–diphenyl–1,2,4–triazine (PDPT) represents a principal class of N–donor heterocyclic ligands that exhibit interesting pharmacological properties such as blood platelet aggregation inhibition, significant activity towards leukemia and ovarian cancer, and anti–HIV activity (Mashaly et al., 1999; Soudi et al., 2005). It also has been widely used as an sensitive reagent for the determination of Fe(II) by spectrophotometric methods, in natural and waste water (Croot & Hunter, 2000). The title complex, was recently prepared and its crystal structure is reported here.

The title compound crystal structure is composed of centrosymmetric binuclear [Cu₂(H₂O)₂(PDPT)₂(C₆H₈O₄)₂] complex molecule (Fig. 1). The dinuclear complex molecules are centered at the crystallographic 2e positions. Each Cu atom is coordinated by two N atoms of the chelating PDPT ligand and three O atoms of one H₂O molecule and two bis–monodentate adipato ligands to form a slightly distorted square–pyramidal coordination with H₂O molecule located at the apical position (d(Cu–N) = 2.028 (3)Å, 2.029 (3)Å, the basal d(Cu–O) = 1.921 (3)Å, 1.961 (3)Å, the axial d(Cu–O) = 2.375 (3)Å). Through the adipato ligands, the square–pyramidally coordinated Cu atoms are linked to form centrosymmetric dinuclear. As expected, the Cu atom is slightly shifted toward the apical water O atom by 0.026 (2)Å from the least–squares plane defined by the four equatorial coordinating atoms. The triazine ring adopts a slight twist conformation. The dihedral angle between the two phenyl rings is 61.9 (2)°.

As shown in the Fig. 2 and Table 1, within the crystal structure, the water molecule O5 forms a strong intramolecular hydrogen bond to the uncoordinated carboxyl O3ⁱ with O5···O3ⁱ = 2.721 (3)Å and angle O5—H5A···O3ⁱ = 161°. Moreover, it forms an intermolecular hydrogen bond to the coordinated carboxyl O1ⁱⁱ atoms with O5···O1ⁱⁱ = 2.878 (4)Å and angle O5—H5B···O1ⁱⁱ = 167° to connect the dinuclear complexes along the [0 1 0] direction. Symmetry codes: (i) -x, -y, -z+1; (ii) -x, -y+1, -z+1.

Related literature top

For the biological activity and applications of triazines, see: Garcia et al. (1995); Mashaly et al. (1999); Croot & Hunter (2000); Soudi et al. (2005); Kawamichi et al. (2009).

Experimental top

Addition of 2.0 mL (1.0 M) NaOH to a stirred aqueous of 0.172 g (1.0 mmol) CuCl₂^.2H₂O in 5.0 mL H₂O yield a blue precipitate, which was then separated by centrifugation, followed by washing with double–distilled water until no detectable Cl^- anions in supernatant. The precipitate was added to a stirred ethanolic aqueous solution of 0.146 g (1.0 mmol) adipic acid in 20 mL EtOH/H₂O (v:v = 1: 1). To the resulting suspension was added 0.310 g (1.0 mmol) 3–(2–pyridyl)–5,6–diphenyl–1,2,4–triazine (PDPT). The mixture was further stirred for approximately 15 min and the insoluble solid was filtered off. The filtrate (pH = 6.5) was allowed to stand at room temperature. Slow evaporation for two weeks afforded a small amount of brown crystals (yield 58% based on the initial CuCl₂^.2H₂O input).

Structure description top

For the biological activity and applications of triazines, see: Garcia et al. (1995); Mashaly et al. (1999); Croot & Hunter (2000); Soudi et al. (2005); Kawamichi et al. (2009).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The binuclear structure of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 40% probability level. H atoms are presented as a small spheres of arbitrary radius. Symmetry code: (i) -x, -y, -z+1.Di-µ-adipato-κ⁴O¹:O⁵-bis{aqua[5,6-diphenyl- 3-(pyridin-2-yl)-1,2,4-triazine-κ²N²,N³]copper(II)}
	Fig. 2. One dimensional chain through hydrogen bond along [0 1 0]. The C—H bonds omitted for clarity.

Di-µ-adipato-κ⁴O¹:O⁶-bis{aqua[5,6-diphenyl-3-(pyridin-2- yl)-1,2,4-triazine-κ²N²,N³]copper(II)} top

Crystal data top

[Cu₂(C₆H₈O₄)₂(C₂₀H₁₄N₄)₂(H₂O)₂]	Z = 1
M_r = 1072.08	F(000) = 554
Triclinic, P1	D_x = 1.501 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4825 (19) Å	Cell parameters from 8025 reflections
b = 10.616 (2) Å	θ = 3.3–27.5°
c = 13.080 (3) Å	µ = 0.97 mm⁻¹
α = 78.96 (3)°	T = 295 K
β = 68.76 (3)°	Plate, brown
γ = 76.85 (3)°	0.30 × 0.19 × 0.11 mm
V = 1186.4 (5) Å³

Data collection top

Rigaku R-AXIS RAPID CCD diffractometer	5295 independent reflections
Radiation source: fine-focus sealed tube	3207 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ω–scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −12→11
T_min = 0.756, T_max = 0.863	k = −13→13
11646 measured reflections	l = −16→16

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0516P)² + 0.8435P] where P = (F_o² + 2F_c²)/3
5295 reflections	(Δ/σ)_max < 0.001
333 parameters	Δρ_max = 0.61 e Å⁻³
3 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

[Cu₂(C₆H₈O₄)₂(C₂₀H₁₄N₄)₂(H₂O)₂]	γ = 76.85 (3)°
M_r = 1072.08	V = 1186.4 (5) Å³
Triclinic, P1	Z = 1
a = 9.4825 (19) Å	Mo Kα radiation
b = 10.616 (2) Å	µ = 0.97 mm⁻¹
c = 13.080 (3) Å	T = 295 K
α = 78.96 (3)°	0.30 × 0.19 × 0.11 mm
β = 68.76 (3)°

Data collection top

Rigaku R-AXIS RAPID CCD diffractometer	5295 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3207 reflections with I > 2σ(I)
T_min = 0.756, T_max = 0.863	R_int = 0.061
11646 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	3 restraints
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.61 e Å⁻³
5295 reflections	Δρ_min = −0.51 e Å⁻³
333 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.24237 (6)	0.28612 (5)	0.46540 (4)	0.03879 (17)
N1	0.4452 (4)	0.2512 (3)	0.4938 (3)	0.0374 (8)
N2	0.3453 (3)	0.4301 (3)	0.3587 (3)	0.0333 (7)
N3	0.5595 (3)	0.5336 (3)	0.3071 (3)	0.0343 (7)
N4	0.3041 (3)	0.4987 (3)	0.2743 (3)	0.0355 (7)
O1	0.0833 (3)	0.3122 (3)	0.3970 (2)	0.0390 (6)
O2	0.2814 (3)	0.1907 (3)	0.2883 (3)	0.0488 (7)
O3	0.0418 (3)	−0.2164 (3)	0.3245 (3)	0.0570 (8)
O4	−0.1845 (3)	−0.1321 (3)	0.4379 (3)	0.0488 (8)
O5	0.0969 (3)	0.4299 (3)	0.5999 (3)	0.0495 (8)
H5A	0.042 (4)	0.375 (3)	0.634 (4)	0.074*
H5B	0.040 (4)	0.501 (2)	0.593 (4)	0.074*
C1	0.4946 (5)	0.1514 (4)	0.5589 (3)	0.0436 (10)
H1A	0.4325	0.0892	0.5955	0.052*
C2	0.6347 (5)	0.1373 (4)	0.5739 (3)	0.0460 (11)
H2A	0.6684	0.0647	0.6170	0.055*
C3	0.7228 (5)	0.2320 (4)	0.5244 (4)	0.0471 (11)
H3A	0.8152	0.2262	0.5362	0.057*
C4	0.6740 (4)	0.3366 (4)	0.4566 (3)	0.0404 (9)
H4A	0.7322	0.4020	0.4221	0.048*
C5	0.5364 (4)	0.3401 (4)	0.4422 (3)	0.0333 (8)
C6	0.7323 (4)	0.7259 (4)	0.1838 (4)	0.0414 (10)
H6A	0.7876	0.6483	0.2068	0.050*
C7	0.7968 (5)	0.8365 (4)	0.1501 (4)	0.0495 (11)
H7A	0.8964	0.8330	0.1486	0.059*
C8	0.7152 (5)	0.9530 (4)	0.1183 (4)	0.0520 (12)
H8A	0.7591	1.0279	0.0959	0.062*
C9	0.5676 (5)	0.9572 (4)	0.1200 (4)	0.0497 (11)
H9A	0.5117	1.0358	0.0996	0.060*
C10	0.5033 (5)	0.8481 (4)	0.1509 (4)	0.0419 (10)
H10A	0.4046	0.8525	0.1502	0.050*
C11	0.5839 (4)	0.7290 (3)	0.1840 (3)	0.0331 (8)
C12	0.2046 (4)	0.6241 (4)	0.1017 (4)	0.0423 (10)
H12A	0.1287	0.6023	0.1676	0.051*
C13	0.1724 (5)	0.6510 (4)	0.0040 (4)	0.0492 (11)
H13A	0.0761	0.6445	0.0043	0.059*
C14	0.2816 (5)	0.6872 (4)	−0.0934 (4)	0.0510 (11)
H14A	0.2587	0.7071	−0.1586	0.061*
C15	0.4258 (5)	0.6942 (4)	−0.0942 (3)	0.0444 (10)
H15A	0.4999	0.7191	−0.1601	0.053*
C16	0.4600 (5)	0.6642 (4)	0.0026 (3)	0.0379 (9)
H16A	0.5579	0.6675	0.0011	0.045*
C17	0.3498 (4)	0.6293 (3)	0.1022 (3)	0.0323 (8)
C18	0.4794 (4)	0.4412 (3)	0.3645 (3)	0.0308 (8)
C19	0.5105 (4)	0.6140 (3)	0.2307 (3)	0.0320 (8)
C20	0.3880 (4)	0.5838 (3)	0.2046 (3)	0.0322 (8)
C21	0.1506 (4)	0.2554 (4)	0.3093 (3)	0.0363 (9)
C22	0.0629 (5)	0.2733 (4)	0.2294 (4)	0.0424 (10)
H22A	−0.0456	0.2783	0.2717	0.051*
H22B	0.0762	0.3559	0.1834	0.051*
C23	0.1097 (5)	0.1676 (4)	0.1553 (3)	0.0441 (10)
H23A	0.2148	0.1694	0.1071	0.053*
H23B	0.0456	0.1878	0.1090	0.053*
C24	0.0991 (5)	0.0304 (4)	0.2136 (4)	0.0525 (11)
H24A	0.1160	−0.0266	0.1590	0.063*
H24B	0.1818	0.0018	0.2443	0.063*
C25	−0.0463 (5)	0.0133 (4)	0.3027 (4)	0.0595 (13)
H25A	−0.1292	0.0445	0.2724	0.071*
H25B	−0.0616	0.0685	0.3583	0.071*
C26	−0.0602 (5)	−0.1238 (4)	0.3594 (3)	0.0393 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0376 (3)	0.0390 (3)	0.0392 (3)	−0.0141 (2)	−0.0134 (2)	0.0069 (2)
N1	0.0387 (18)	0.0370 (18)	0.034 (2)	−0.0073 (14)	−0.0125 (15)	0.0035 (15)
N2	0.0339 (16)	0.0338 (17)	0.0325 (19)	−0.0103 (13)	−0.0124 (14)	0.0033 (14)
N3	0.0330 (17)	0.0318 (17)	0.036 (2)	−0.0066 (13)	−0.0103 (14)	−0.0015 (14)
N4	0.0364 (17)	0.0380 (18)	0.0308 (19)	−0.0067 (14)	−0.0130 (14)	0.0026 (14)
O1	0.0372 (14)	0.0379 (15)	0.0414 (18)	−0.0135 (12)	−0.0097 (13)	−0.0023 (13)
O2	0.0369 (16)	0.0528 (18)	0.058 (2)	−0.0044 (14)	−0.0162 (14)	−0.0125 (15)
O3	0.0568 (19)	0.0408 (17)	0.061 (2)	−0.0117 (15)	−0.0073 (16)	0.0011 (16)
O4	0.0459 (17)	0.0403 (16)	0.050 (2)	−0.0119 (13)	−0.0076 (15)	0.0081 (14)
O5	0.0481 (18)	0.0387 (16)	0.056 (2)	−0.0060 (13)	−0.0129 (16)	−0.0035 (15)
C1	0.045 (2)	0.041 (2)	0.037 (3)	−0.0053 (18)	−0.0106 (19)	0.0029 (19)
C2	0.045 (2)	0.050 (3)	0.035 (3)	0.007 (2)	−0.016 (2)	−0.001 (2)
C3	0.034 (2)	0.062 (3)	0.044 (3)	0.000 (2)	−0.015 (2)	−0.010 (2)
C4	0.038 (2)	0.041 (2)	0.043 (3)	−0.0060 (18)	−0.0153 (19)	−0.0050 (19)
C5	0.035 (2)	0.034 (2)	0.029 (2)	−0.0043 (16)	−0.0095 (17)	−0.0043 (16)
C6	0.037 (2)	0.036 (2)	0.048 (3)	−0.0079 (17)	−0.0110 (19)	−0.0018 (19)
C7	0.045 (2)	0.046 (2)	0.060 (3)	−0.020 (2)	−0.012 (2)	−0.007 (2)
C8	0.069 (3)	0.037 (2)	0.055 (3)	−0.027 (2)	−0.018 (2)	0.001 (2)
C9	0.068 (3)	0.030 (2)	0.054 (3)	−0.009 (2)	−0.026 (2)	0.001 (2)
C10	0.046 (2)	0.033 (2)	0.050 (3)	−0.0080 (17)	−0.019 (2)	−0.0043 (19)
C11	0.037 (2)	0.0273 (18)	0.035 (2)	−0.0111 (15)	−0.0100 (17)	−0.0014 (16)
C12	0.035 (2)	0.050 (2)	0.037 (2)	−0.0076 (18)	−0.0116 (18)	0.0057 (19)
C13	0.042 (2)	0.058 (3)	0.047 (3)	−0.004 (2)	−0.021 (2)	0.001 (2)
C14	0.064 (3)	0.046 (3)	0.039 (3)	0.002 (2)	−0.023 (2)	0.000 (2)
C15	0.057 (3)	0.036 (2)	0.029 (2)	−0.0072 (19)	−0.002 (2)	−0.0014 (18)
C16	0.040 (2)	0.033 (2)	0.037 (2)	−0.0084 (16)	−0.0085 (18)	−0.0025 (17)
C17	0.041 (2)	0.0256 (18)	0.031 (2)	−0.0087 (15)	−0.0126 (17)	−0.0012 (16)
C18	0.0319 (19)	0.0302 (19)	0.029 (2)	−0.0081 (15)	−0.0077 (16)	−0.0034 (16)
C19	0.0287 (18)	0.0308 (19)	0.032 (2)	−0.0051 (15)	−0.0064 (16)	−0.0005 (16)
C20	0.0288 (18)	0.0264 (18)	0.037 (2)	−0.0041 (15)	−0.0071 (16)	−0.0027 (16)
C21	0.036 (2)	0.031 (2)	0.042 (3)	−0.0163 (17)	−0.0109 (18)	0.0036 (18)
C22	0.046 (2)	0.038 (2)	0.043 (3)	−0.0154 (18)	−0.017 (2)	0.0094 (19)
C23	0.049 (2)	0.052 (3)	0.034 (2)	−0.021 (2)	−0.016 (2)	0.008 (2)
C24	0.064 (3)	0.048 (3)	0.041 (3)	−0.020 (2)	−0.006 (2)	−0.007 (2)
C25	0.059 (3)	0.046 (3)	0.062 (4)	−0.013 (2)	−0.007 (3)	−0.002 (2)
C26	0.046 (2)	0.034 (2)	0.038 (3)	−0.0121 (18)	−0.014 (2)	−0.0003 (18)

Geometric parameters (Å, º) top

Cu1—O1	1.961 (3)	C8—C9	1.382 (6)
Cu1—O4ⁱ	1.921 (3)	C8—H8A	0.9300
Cu1—O5	2.375 (3)	C9—C10	1.356 (6)
Cu1—N1	2.029 (3)	C9—H9A	0.9300
Cu1—N2	2.028 (3)	C10—C11	1.401 (5)
N1—C1	1.336 (5)	C10—H10A	0.9300
N1—C5	1.341 (5)	C11—C19	1.463 (5)
N2—C18	1.333 (4)	C12—C13	1.382 (6)
N2—N4	1.334 (4)	C12—C17	1.394 (5)
N3—C18	1.321 (5)	C12—H12A	0.9300
N3—C19	1.332 (4)	C13—C14	1.371 (6)
N4—C20	1.329 (5)	C13—H13A	0.9300
O1—C21	1.283 (5)	C14—C15	1.382 (6)
O2—C21	1.235 (4)	C14—H14A	0.9300
O3—C26	1.236 (5)	C15—C16	1.380 (6)
O4—C26	1.260 (5)	C15—H15A	0.9300
O4—Cu1ⁱ	1.921 (3)	C16—C17	1.390 (5)
O5—H5A	0.829 (18)	C16—H16A	0.9300
O5—H5B	0.830 (18)	C17—C20	1.477 (5)
C1—C2	1.383 (5)	C19—C20	1.438 (5)
C1—H1A	0.9300	C21—C22	1.516 (5)
C2—C3	1.367 (6)	C22—C23	1.508 (6)
C2—H2A	0.9300	C22—H22A	0.9700
C3—C4	1.385 (6)	C22—H22B	0.9700
C3—H3A	0.9300	C23—C24	1.516 (6)
C4—C5	1.376 (5)	C23—H23A	0.9700
C4—H4A	0.9300	C23—H23B	0.9700
C5—C18	1.481 (5)	C24—C25	1.470 (6)
C6—C7	1.372 (6)	C24—H24A	0.9700
C6—C11	1.399 (5)	C24—H24B	0.9700
C6—H6A	0.9300	C25—C26	1.513 (6)
C7—C8	1.378 (6)	C25—H25A	0.9700
C7—H7A	0.9300	C25—H25B	0.9700

O1—Cu1—O5	94.47 (11)	C13—C12—H12A	119.7
O1—Cu1—N1	164.40 (13)	C17—C12—H12A	119.7
O1—Cu1—N2	92.22 (11)	C14—C13—C12	120.4 (4)
O4ⁱ—Cu1—O1	96.02 (12)	C14—C13—H13A	119.8
O4ⁱ—Cu1—O5	94.45 (12)	C12—C13—H13A	119.8
O4ⁱ—Cu1—N1	90.71 (12)	C13—C14—C15	119.8 (4)
O4ⁱ—Cu1—N2	168.98 (12)	C13—C14—H14A	120.1
N1—Cu1—O5	99.04 (12)	C15—C14—H14A	120.1
N2—Cu1—O5	92.19 (12)	C16—C15—C14	120.1 (4)
N2—Cu1—N1	79.55 (12)	C16—C15—H15A	120.0
C1—N1—C5	117.8 (3)	C14—C15—H15A	120.0
C1—N1—Cu1	126.9 (3)	C15—C16—C17	120.8 (4)
C5—N1—Cu1	115.3 (2)	C15—C16—H16A	119.6
C18—N2—N4	117.7 (3)	C17—C16—H16A	119.6
C18—N2—Cu1	115.4 (2)	C16—C17—C12	118.3 (3)
N4—N2—Cu1	126.0 (2)	C16—C17—C20	121.7 (3)
C18—N3—C19	117.8 (3)	C12—C17—C20	119.6 (3)
C20—N4—N2	120.5 (3)	N3—C18—N2	124.6 (3)
C21—O1—Cu1	104.0 (2)	N3—C18—C5	120.5 (3)
C26—O4—Cu1ⁱ	126.9 (3)	N2—C18—C5	114.9 (3)
Cu1—O5—H5A	90 (4)	N3—C19—C20	118.0 (3)
Cu1—O5—H5B	129 (4)	N3—C19—C11	115.9 (3)
H5A—O5—H5B	108 (3)	C20—C19—C11	126.0 (3)
N1—C1—C2	122.4 (4)	N4—C20—C19	118.7 (3)
N1—C1—H1A	118.8	N4—C20—C17	114.1 (3)
C2—C1—H1A	118.8	C19—C20—C17	127.0 (3)
C3—C2—C1	118.8 (4)	O2—C21—O1	122.7 (4)
C3—C2—H2A	120.6	O2—C21—C22	120.5 (4)
C1—C2—H2A	120.6	O1—C21—C22	116.8 (3)
C2—C3—C4	119.8 (4)	C23—C22—C21	115.3 (3)
C2—C3—H3A	120.1	C23—C22—H22A	108.5
C4—C3—H3A	120.1	C21—C22—H22A	108.5
C5—C4—C3	117.6 (4)	C23—C22—H22B	108.5
C5—C4—H4A	121.2	C21—C22—H22B	108.5
C3—C4—H4A	121.2	H22A—C22—H22B	107.5
N1—C5—C4	123.4 (3)	C22—C23—C24	115.8 (4)
N1—C5—C18	114.3 (3)	C22—C23—H23A	108.3
C4—C5—C18	122.2 (4)	C24—C23—H23A	108.3
C7—C6—C11	120.4 (4)	C22—C23—H23B	108.3
C7—C6—H6A	119.8	C24—C23—H23B	108.3
C11—C6—H6A	119.8	H23A—C23—H23B	107.4
C6—C7—C8	120.6 (4)	C25—C24—C23	116.0 (4)
C6—C7—H7A	119.7	C25—C24—H24A	108.3
C8—C7—H7A	119.7	C23—C24—H24A	108.3
C7—C8—C9	119.3 (4)	C25—C24—H24B	108.3
C7—C8—H8A	120.3	C23—C24—H24B	108.3
C9—C8—H8A	120.3	H24A—C24—H24B	107.4
C10—C9—C8	120.9 (4)	C24—C25—C26	116.6 (4)
C10—C9—H9A	119.6	C24—C25—H25A	108.2
C8—C9—H9A	119.6	C26—C25—H25A	108.2
C9—C10—C11	120.7 (4)	C24—C25—H25B	108.2
C9—C10—H10A	119.6	C26—C25—H25B	108.2
C11—C10—H10A	119.6	H25A—C25—H25B	107.3
C6—C11—C10	118.1 (3)	O3—C26—O4	125.7 (4)
C6—C11—C19	119.8 (3)	O3—C26—C25	120.3 (4)
C10—C11—C19	121.6 (3)	O4—C26—C25	113.9 (4)
C13—C12—C17	120.5 (4)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O3ⁱ	0.83	1.92	2.721 (3)	161
O5—H5B···O1ⁱⁱ	0.83	2.06	2.878 (4)	167

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

Experimental details

Crystal data
Chemical formula	[Cu₂(C₆H₈O₄)₂(C₂₀H₁₄N₄)₂(H₂O)₂]
M_r	1072.08
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	9.4825 (19), 10.616 (2), 13.080 (3)
α, β, γ (°)	78.96 (3), 68.76 (3), 76.85 (3)
V (Å³)	1186.4 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.30 × 0.19 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS RAPID CCD
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.756, 0.863
No. of measured, independent and observed [I > 2σ(I)] reflections	11646, 5295, 3207
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.135, 1.02
No. of reflections	5295
No. of parameters	333
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.51

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), 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—H5A···O3ⁱ	0.83	1.92	2.721 (3)	161
O5—H5B···O1ⁱⁱ	0.83	2.06	2.878 (4)	167

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

Acknowledgements

This project was sponsored by the K. C. Wong Magna Fund in Ningbo University.

References

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