Poly[[diaqua­bis­{μ-4-[6-(4-carb­oxy­phen­yl)-4,4′-bipyridin-2-yl]benzoato-κ2O:N1′}copper(II)] dimethyl­formamide tetra­solvate]

Sun, Y.; Song, E.; Wang, D.

doi:10.1107/S1600536813006430

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Pages m202-m203

doi:10.1107/S1600536813006430

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Poly[[diaquabis{μ-4-[6-(4-carboxyphenyl)-4,4′-bipyridin-2-yl]benzoato-κ²O:N^1′}copper(II)] dimethylformamide tetrasolvate]

Yabin Sun,^a E Song ^a and Daguang Wang ^b ^*

^aDepartment of Ophthalmology, The First Hospital of Jilin University, Changchun, 130021, People's Republic of China, and ^bDepartment of Gastrointestinal Surgery, The First Hospital of Jilin University, Changchun, 130021, People's Republic of China
^*Correspondence e-mail: doctorwangdg@163.com

(Received 28 February 2013; accepted 6 March 2013; online 13 March 2013)

In the title compound, {[Cu(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO}_n, the Cu^II ion, lying on an inversion center, is six-coordinated by two N atoms from two 4-[6-(4-carboxyphenyl)-4,4′-bipyridin-2-yl]benzoate (L) ligands, two deprotonated carboxylate O atoms from two other symmetry-related L ligands and two water molecules in a slightly distorted octahedral geometry. The Cu^II atoms are linked by the bridging ligands into a layer parallel to (101). The presence of intralayer O—H⋯O hydrogen bonds and π–π interactions between the pyridine and benzene rings [centroid–centroid distances = 3.808 (2) and 3.927 (2) Å] stabilizes the layer. Further O—H⋯O hydrogen bonds link the layers and the dimethylformamide solvent molecules.

Related literature

For the design of metal-organic coordination polymers, see: Ge & Song (2012 ); Herm et al. (2011 ); Liu et al. (2010 ); Wang et al. (2010 ). For a related structure, see: Xia et al. (2012 ).

Experimental

Crystal data

[Cu(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO
M_r = 1182.73
Monoclinic, P 2₁ /n
a = 7.7161 (17) Å
b = 17.550 (4) Å
c = 20.947 (4) Å
β = 96.800 (4)°
V = 2816.6 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 293 K
0.27 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.885, T_max = 0.913
14622 measured reflections
5226 independent reflections
3371 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.185
S = 1.04
5226 reflections
376 parameters
H-atom parameters constrained
Δρ_max = 0.93 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O2ⁱ	0.82	1.86	2.584 (4)	146
O1W—H1A⋯O5ⁱⁱ	0.85	1.98	2.808 (5)	165
O1W—H1B⋯O2ⁱⁱⁱ	0.85	1.95	2.758 (4)	159
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813006430/hy2619sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813006430/hy2619Isup2.hkl

checkCIF report

Comment top

Metal-organic coordination polymers (MOCPs) with infinite one-, two- or three-dimensional structures are assembled with metal ions or polynuclear clusters as nodes and organic ligands as linkers (Herm et al., 2011; Liu et al., 2010). Recently, the chemists have devoted themselves to design and synthesize MOCPs, not only due to their potential applications in the realm of gas adsorption and separation, catalysis, magnetism, luminescence, host–guest chemistry and etc, but also for their aesthetic and often complicated architectures and topologies (Ge & Song, 2012; Wang et al., 2010). In order to extend the investigations in this field, we used a multifunctional ligand, 4,4'-(4,4'-bipyridine-2,6-diyl)dibenzoic acid (bpydbH₂) to design and synthesize the title copper(II) complex and report its structure here.

The asymmetric unit of the title compound contains one Cu^II ion lying on an inversion center, one anionic bpydbH ligand, one aqua ligand and two lattice DMF molecules. As shown in Fig. 1, the Cu^II ion is six-coordinated by two N atoms from two bpydbH ligands, two deprotonated carboxylate O atoms from two other symmetry-related bpydbH ligands and two aqua ligands, furnishing a slightly distorted octahedral geometry. The bond distances and angles are in a normal range (Xia et al., 2012). The Cu nodes are extended by the bridging bpydbH linkers into a layer parallel to (101) (Fig. 2). The presence of intralayer O—H···O hydrogen bonds and π–π interactions between the pyridine and benzene rings [centroid–centroid diatances = 3.808 (2) and 3.927 (2) Å] stabilizes the single layer.

Related literature top

For the design of metal-organic coordination polymers, see: Ge & Song (2012); Herm et al. (2011); Liu et al. (2010); Wang et al. (2010). For a related structure, see: Xia et al. (2012).

Experimental top

Cu(NO₃)₂.3H₂O (0.0063 g, 0.025 mmol) and bpydbH₂ (0.0099 g, 0.025 mmol) were suspended in a mixed solvent of dimethylformamide (DMF) (4 ml) and H₂O (0.5 ml), and heated in a 15 ml Teflon-lined stainless-steel autoclave at 80°C for 3 days. After the autoclave was cooled to room temperature slowly, green crystals were collected by filtration and washed with DMF, and dried in air (yield: 65% based on Cu).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: XP in SHELXTL and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 1/2 + x, 3/2 - y, -1/2 + z; (ii) 3/2 - x, -1/2 + y, 1/2 - z; (iii) 2 - x, 1 - y, -z.]
	Fig. 2. View of the layer structure of the title compound.

Poly[[diaquabis{µ-4-[6-(4-carboxyphenyl)-4,4'-bipyridin-2-yl]benzoato-κ²O:N^1'}copper(II)] dimethylformamide tetrasolvate] top

Crystal data top

[Cu(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO	F(000) = 1238
M_r = 1182.73	D_x = 1.395 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5226 reflections
a = 7.7161 (17) Å	θ = 1.0–26.0°
b = 17.550 (4) Å	µ = 0.46 mm⁻¹
c = 20.947 (4) Å	T = 293 K
β = 96.800 (4)°	Block, green
V = 2816.6 (10) Å³	0.27 × 0.25 × 0.20 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	5226 independent reflections
Radiation source: fine-focus sealed tube	3371 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→7
T_min = 0.885, T_max = 0.913	k = −21→21
14622 measured reflections	l = −20→25

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.185	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0891P)² + 2.0095P] where P = (F_o² + 2F_c²)/3
5226 reflections	(Δ/σ)_max < 0.001
376 parameters	Δρ_max = 0.93 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Cu(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO	V = 2816.6 (10) Å³
M_r = 1182.73	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.7161 (17) Å	µ = 0.46 mm⁻¹
b = 17.550 (4) Å	T = 293 K
c = 20.947 (4) Å	0.27 × 0.25 × 0.20 mm
β = 96.800 (4)°

Data collection top

Bruker APEXII CCD diffractometer	5226 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3371 reflections with I > 2σ(I)
T_min = 0.885, T_max = 0.913	R_int = 0.058
14622 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.185	H-atom parameters constrained
S = 1.04	Δρ_max = 0.93 e Å⁻³
5226 reflections	Δρ_min = −0.39 e Å⁻³
376 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	1.0000	0.5000	0.0000	0.0362 (2)
C1	0.8452 (6)	1.2336 (2)	−0.1386 (2)	0.0432 (10)
C2	0.8060 (5)	1.1653 (2)	−0.10151 (19)	0.0347 (9)
C3	0.7251 (5)	1.1715 (2)	−0.0455 (2)	0.0369 (10)
H3	0.6854	1.2186	−0.0330	0.044*
C4	0.7040 (5)	1.1079 (2)	−0.0088 (2)	0.0350 (9)
H4	0.6517	1.1128	0.0288	0.042*
C5	0.7592 (5)	1.0363 (2)	−0.02669 (18)	0.0286 (8)
C6	0.8380 (5)	1.0305 (2)	−0.08253 (19)	0.0352 (9)
H6	0.8762	0.9832	−0.0953	0.042*
C7	0.8607 (5)	1.0943 (2)	−0.11976 (19)	0.0376 (10)
H7	0.9132	1.0894	−0.1573	0.045*
C8	0.7389 (5)	0.9695 (2)	0.01565 (19)	0.0302 (8)
C9	0.7683 (5)	0.8950 (2)	−0.00365 (18)	0.0304 (9)
H9	0.7972	0.8853	−0.0447	0.036*
C10	0.7540 (5)	0.83558 (19)	0.03927 (18)	0.0280 (8)
C11	0.7072 (5)	0.8537 (2)	0.09959 (18)	0.0314 (9)
H11	0.6958	0.8154	0.1295	0.038*
C12	0.6774 (5)	0.9291 (2)	0.11507 (18)	0.0299 (8)
C13	0.6253 (5)	0.9511 (2)	0.17864 (18)	0.0301 (9)
C14	0.5242 (5)	1.0156 (2)	0.18392 (19)	0.0358 (9)
H14	0.4924	1.0455	0.1478	0.043*
C15	0.4702 (5)	1.0358 (2)	0.24194 (19)	0.0372 (10)
H15	0.4004	1.0786	0.2445	0.045*
C16	0.5196 (5)	0.9925 (2)	0.29668 (18)	0.0312 (9)
C17	0.6242 (5)	0.9290 (2)	0.29215 (19)	0.0378 (10)
H17	0.6586	0.8998	0.3285	0.045*
C18	0.6777 (5)	0.9089 (2)	0.23352 (19)	0.0366 (9)
H18	0.7494	0.8667	0.2310	0.044*
C19	0.4600 (6)	1.0145 (2)	0.3597 (2)	0.0361 (10)
C20	0.7944 (5)	0.75539 (19)	0.02344 (17)	0.0288 (8)
C21	0.9191 (5)	0.73870 (19)	−0.01677 (18)	0.0307 (9)
H21	0.9689	0.7778	−0.0384	0.037*
C22	0.9695 (5)	0.6647 (2)	−0.02478 (19)	0.0339 (9)
H22	1.0543	0.6549	−0.0517	0.041*
C23	0.7732 (5)	0.6214 (2)	0.04100 (19)	0.0360 (9)
H23	0.7197	0.5811	0.0598	0.043*
C24	0.7177 (5)	0.6942 (2)	0.05158 (18)	0.0342 (9)
H24	0.6294	0.7025	0.0774	0.041*
C25	0.6692 (8)	0.6406 (4)	−0.1720 (3)	0.0829 (19)
H25A	0.7059	0.6773	−0.2016	0.124*
H25B	0.6144	0.5984	−0.1955	0.124*
H25C	0.7689	0.6229	−0.1442	0.124*
C26	0.5118 (8)	0.7558 (3)	−0.1443 (3)	0.0756 (16)
H26A	0.5739	0.7741	−0.1783	0.113*
H26B	0.5493	0.7833	−0.1055	0.113*
H26C	0.3889	0.7633	−0.1558	0.113*
C27	0.4770 (6)	0.6364 (3)	−0.0897 (2)	0.0543 (12)
H27	0.5082	0.5854	−0.0843	0.065*
C28	0.4517 (16)	1.2769 (5)	−0.2557 (5)	0.203 (6)
H28A	0.4153	1.2642	−0.2148	0.304*
H28B	0.5656	1.2561	−0.2586	0.304*
H28C	0.3703	1.2562	−0.2895	0.304*
C29	0.4063 (11)	1.3970 (6)	−0.2090 (4)	0.157 (4)
H29A	0.3787	1.3613	−0.1770	0.235*
H29B	0.3054	1.4274	−0.2228	0.235*
H29C	0.4999	1.4294	−0.1912	0.235*
C30	0.5028 (11)	1.3864 (4)	−0.3123 (4)	0.119 (3)
H30	0.4860	1.4387	−0.3166	0.142*
N1	0.6925 (4)	0.98644 (16)	0.07362 (15)	0.0305 (7)
N2	0.9010 (4)	0.60580 (17)	0.00477 (15)	0.0331 (8)
N3	0.5471 (5)	0.6755 (2)	−0.13415 (19)	0.0533 (10)
N4	0.4576 (6)	1.3570 (2)	−0.2622 (2)	0.0619 (11)
O1	0.5313 (4)	0.98064 (14)	0.40897 (13)	0.0395 (7)
O2	0.3418 (4)	1.06386 (16)	0.35908 (14)	0.0488 (8)
O3	0.9397 (5)	1.23445 (17)	−0.18056 (16)	0.0582 (9)
O4	0.7673 (4)	1.29571 (17)	−0.11906 (16)	0.0607 (9)
H4A	0.7916	1.3324	−0.1405	0.091*
O5	0.3740 (4)	0.6624 (2)	−0.05498 (17)	0.0651 (10)
O6	0.5670 (7)	1.3545 (2)	−0.3567 (2)	0.1082 (17)
O1W	1.3019 (4)	0.54357 (17)	0.02770 (15)	0.0552 (8)
H1A	1.3236	0.5847	0.0087	0.083*
H1B	1.2828	0.5552	0.0656	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0628 (5)	0.0222 (3)	0.0263 (4)	0.0050 (3)	0.0164 (3)	0.0015 (3)
C1	0.054 (3)	0.033 (2)	0.042 (3)	−0.001 (2)	0.005 (2)	0.0034 (19)
C2	0.036 (2)	0.031 (2)	0.037 (2)	−0.0049 (17)	0.0019 (18)	0.0061 (17)
C3	0.040 (2)	0.0251 (19)	0.046 (3)	0.0037 (16)	0.010 (2)	0.0004 (17)
C4	0.039 (2)	0.0273 (19)	0.041 (2)	0.0008 (17)	0.0146 (19)	0.0013 (17)
C5	0.032 (2)	0.0272 (19)	0.027 (2)	−0.0010 (16)	0.0060 (16)	0.0009 (15)
C6	0.048 (2)	0.0254 (18)	0.033 (2)	0.0009 (17)	0.0094 (19)	−0.0029 (16)
C7	0.052 (3)	0.035 (2)	0.028 (2)	−0.0037 (18)	0.0104 (19)	0.0002 (17)
C8	0.034 (2)	0.0256 (18)	0.032 (2)	0.0004 (16)	0.0066 (17)	0.0011 (16)
C9	0.037 (2)	0.0284 (19)	0.027 (2)	0.0006 (16)	0.0088 (17)	−0.0017 (16)
C10	0.033 (2)	0.0240 (18)	0.028 (2)	−0.0001 (15)	0.0067 (16)	−0.0014 (15)
C11	0.042 (2)	0.0257 (19)	0.027 (2)	0.0008 (16)	0.0090 (17)	0.0019 (16)
C12	0.036 (2)	0.0275 (19)	0.027 (2)	−0.0004 (16)	0.0085 (17)	0.0000 (16)
C13	0.038 (2)	0.0284 (19)	0.025 (2)	−0.0028 (16)	0.0074 (17)	−0.0047 (15)
C14	0.048 (2)	0.033 (2)	0.027 (2)	0.0025 (17)	0.0097 (19)	0.0007 (16)
C15	0.050 (2)	0.030 (2)	0.034 (2)	0.0050 (18)	0.0104 (19)	−0.0020 (17)
C16	0.041 (2)	0.0259 (19)	0.029 (2)	−0.0039 (16)	0.0126 (17)	−0.0045 (16)
C17	0.051 (3)	0.032 (2)	0.032 (2)	0.0009 (18)	0.0092 (19)	0.0052 (17)
C18	0.047 (2)	0.031 (2)	0.033 (2)	0.0078 (18)	0.0118 (19)	−0.0013 (17)
C19	0.050 (2)	0.026 (2)	0.035 (2)	−0.0054 (18)	0.014 (2)	−0.0043 (17)
C20	0.039 (2)	0.0239 (18)	0.024 (2)	0.0012 (16)	0.0051 (16)	−0.0003 (15)
C21	0.043 (2)	0.0225 (18)	0.029 (2)	−0.0019 (16)	0.0141 (17)	0.0005 (15)
C22	0.047 (2)	0.0275 (19)	0.030 (2)	−0.0006 (17)	0.0146 (18)	−0.0004 (16)
C23	0.052 (3)	0.028 (2)	0.030 (2)	−0.0039 (18)	0.0140 (19)	0.0014 (16)
C24	0.045 (2)	0.031 (2)	0.029 (2)	0.0012 (17)	0.0158 (18)	−0.0017 (16)
C25	0.081 (4)	0.119 (5)	0.052 (4)	0.025 (4)	0.022 (3)	0.004 (3)
C26	0.097 (4)	0.062 (3)	0.069 (4)	−0.003 (3)	0.017 (3)	0.009 (3)
C27	0.056 (3)	0.053 (3)	0.054 (3)	−0.005 (2)	0.005 (3)	−0.002 (2)
C28	0.303 (15)	0.088 (6)	0.196 (11)	−0.064 (8)	−0.057 (10)	0.066 (7)
C29	0.132 (7)	0.259 (12)	0.082 (6)	0.104 (8)	0.025 (5)	0.000 (6)
C30	0.167 (8)	0.079 (5)	0.123 (7)	0.022 (5)	0.067 (6)	0.031 (5)
N1	0.0353 (17)	0.0303 (17)	0.0272 (18)	−0.0014 (13)	0.0090 (14)	−0.0030 (13)
N2	0.049 (2)	0.0260 (16)	0.0265 (18)	0.0009 (14)	0.0128 (15)	0.0000 (13)
N3	0.054 (2)	0.062 (3)	0.046 (2)	0.000 (2)	0.0151 (19)	0.0015 (19)
N4	0.071 (3)	0.059 (3)	0.061 (3)	0.012 (2)	0.027 (2)	0.019 (2)
O1	0.0655 (19)	0.0274 (14)	0.0276 (16)	−0.0003 (13)	0.0135 (14)	−0.0001 (11)
O2	0.071 (2)	0.0377 (16)	0.0413 (19)	0.0105 (15)	0.0232 (15)	−0.0045 (13)
O3	0.082 (2)	0.0458 (19)	0.051 (2)	−0.0038 (17)	0.0217 (19)	0.0064 (15)
O4	0.081 (2)	0.0349 (17)	0.070 (2)	0.0016 (16)	0.0251 (19)	0.0134 (16)
O5	0.060 (2)	0.075 (2)	0.064 (2)	−0.0093 (18)	0.0235 (19)	−0.0012 (19)
O6	0.179 (5)	0.077 (3)	0.083 (3)	−0.005 (3)	0.075 (3)	−0.021 (2)
O1W	0.072 (2)	0.0441 (18)	0.053 (2)	−0.0041 (16)	0.0239 (17)	−0.0006 (15)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	1.980 (3)	C19—O2	1.256 (5)
Cu1—O1ⁱⁱ	1.980 (3)	C19—O1	1.260 (5)
Cu1—N2	2.015 (3)	C20—C21	1.383 (5)
Cu1—N2ⁱⁱⁱ	2.015 (3)	C20—C24	1.390 (5)
C1—O3	1.207 (5)	C21—C22	1.371 (5)
C1—O4	1.332 (5)	C21—H21	0.9300
C1—C2	1.480 (5)	C22—N2	1.345 (5)
C2—C7	1.383 (5)	C22—H22	0.9300
C2—C3	1.398 (5)	C23—N2	1.342 (5)
C3—C4	1.375 (5)	C23—C24	1.374 (5)
C3—H3	0.9300	C23—H23	0.9300
C4—C5	1.393 (5)	C24—H24	0.9300
C4—H4	0.9300	C25—N3	1.439 (6)
C5—C6	1.385 (5)	C25—H25A	0.9600
C5—C8	1.490 (5)	C25—H25B	0.9600
C6—C7	1.388 (5)	C25—H25C	0.9600
C6—H6	0.9300	C26—N3	1.447 (6)
C7—H7	0.9300	C26—H26A	0.9600
C8—N1	1.340 (5)	C26—H26B	0.9600
C8—C9	1.394 (5)	C26—H26C	0.9600
C9—C10	1.390 (5)	C27—O5	1.226 (5)
C9—H9	0.9300	C27—N3	1.323 (6)
C10—C11	1.392 (5)	C27—H27	0.9300
C10—C20	1.487 (5)	C28—N4	1.413 (9)
C11—C12	1.388 (5)	C28—H28A	0.9600
C11—H11	0.9300	C28—H28B	0.9600
C12—N1	1.343 (5)	C28—H28C	0.9600
C12—C13	1.487 (5)	C29—N4	1.411 (8)
C13—C14	1.385 (5)	C29—H29A	0.9600
C13—C18	1.387 (5)	C29—H29B	0.9600
C14—C15	1.377 (5)	C29—H29C	0.9600
C14—H14	0.9300	C30—O6	1.238 (8)
C15—C16	1.391 (5)	C30—N4	1.255 (7)
C15—H15	0.9300	C30—H30	0.9300
C16—C17	1.385 (5)	O1—Cu1^iv	1.980 (3)
C16—C19	1.499 (5)	O4—H4A	0.8200
C17—C18	1.387 (5)	O1W—H1A	0.8501
C17—H17	0.9300	O1W—H1B	0.8489
C18—H18	0.9300

O1ⁱ—Cu1—O1ⁱⁱ	180.0	O2—C19—C16	117.9 (4)
O1ⁱ—Cu1—N2	91.16 (11)	O1—C19—C16	116.7 (4)
O1ⁱⁱ—Cu1—N2	88.84 (11)	C21—C20—C24	117.2 (3)
O1ⁱ—Cu1—N2ⁱⁱⁱ	88.84 (11)	C21—C20—C10	121.0 (3)
O1ⁱⁱ—Cu1—N2ⁱⁱⁱ	91.16 (11)	C24—C20—C10	121.7 (3)
N2—Cu1—N2ⁱⁱⁱ	180.0	C22—C21—C20	120.2 (3)
O3—C1—O4	123.2 (4)	C22—C21—H21	119.9
O3—C1—C2	124.8 (4)	C20—C21—H21	119.9
O4—C1—C2	112.0 (4)	N2—C22—C21	122.6 (4)
C7—C2—C3	118.9 (3)	N2—C22—H22	118.7
C7—C2—C1	119.8 (4)	C21—C22—H22	118.7
C3—C2—C1	121.1 (4)	N2—C23—C24	123.0 (3)
C4—C3—C2	120.0 (4)	N2—C23—H23	118.5
C4—C3—H3	120.0	C24—C23—H23	118.5
C2—C3—H3	120.0	C23—C24—C20	119.6 (4)
C3—C4—C5	121.4 (4)	C23—C24—H24	120.2
C3—C4—H4	119.3	C20—C24—H24	120.2
C5—C4—H4	119.3	N3—C25—H25A	109.5
C6—C5—C4	118.3 (3)	N3—C25—H25B	109.5
C6—C5—C8	122.2 (3)	H25A—C25—H25B	109.5
C4—C5—C8	119.5 (3)	N3—C25—H25C	109.5
C5—C6—C7	120.8 (4)	H25A—C25—H25C	109.5
C5—C6—H6	119.6	H25B—C25—H25C	109.5
C7—C6—H6	119.6	N3—C26—H26A	109.5
C2—C7—C6	120.6 (4)	N3—C26—H26B	109.5
C2—C7—H7	119.7	H26A—C26—H26B	109.5
C6—C7—H7	119.7	N3—C26—H26C	109.5
N1—C8—C9	122.8 (3)	H26A—C26—H26C	109.5
N1—C8—C5	115.0 (3)	H26B—C26—H26C	109.5
C9—C8—C5	122.2 (3)	O5—C27—N3	124.9 (5)
C10—C9—C8	119.2 (3)	O5—C27—H27	117.6
C10—C9—H9	120.4	N3—C27—H27	117.6
C8—C9—H9	120.4	N4—C28—H28A	109.5
C9—C10—C11	117.7 (3)	N4—C28—H28B	109.5
C9—C10—C20	122.1 (3)	H28A—C28—H28B	109.5
C11—C10—C20	120.2 (3)	N4—C28—H28C	109.5
C12—C11—C10	119.9 (3)	H28A—C28—H28C	109.5
C12—C11—H11	120.1	H28B—C28—H28C	109.5
C10—C11—H11	120.1	N4—C29—H29A	109.5
N1—C12—C11	122.3 (3)	N4—C29—H29B	109.5
N1—C12—C13	115.9 (3)	H29A—C29—H29B	109.5
C11—C12—C13	121.8 (3)	N4—C29—H29C	109.5
C14—C13—C18	118.8 (3)	H29A—C29—H29C	109.5
C14—C13—C12	119.9 (3)	H29B—C29—H29C	109.5
C18—C13—C12	121.3 (3)	O6—C30—N4	128.2 (7)
C15—C14—C13	120.9 (4)	O6—C30—H30	115.9
C15—C14—H14	119.6	N4—C30—H30	115.9
C13—C14—H14	119.6	C8—N1—C12	118.2 (3)
C14—C15—C16	120.3 (4)	C23—N2—C22	117.3 (3)
C14—C15—H15	119.9	C23—N2—Cu1	121.6 (2)
C16—C15—H15	119.9	C22—N2—Cu1	120.9 (3)
C17—C16—C15	119.2 (4)	C27—N3—C25	121.1 (5)
C17—C16—C19	120.7 (4)	C27—N3—C26	121.6 (4)
C15—C16—C19	120.1 (3)	C25—N3—C26	117.3 (4)
C16—C17—C18	120.2 (4)	C30—N4—C29	125.9 (7)
C16—C17—H17	119.9	C30—N4—C28	120.2 (7)
C18—C17—H17	119.9	C29—N4—C28	113.8 (7)
C17—C18—C13	120.6 (4)	C19—O1—Cu1^iv	128.1 (3)
C17—C18—H18	119.7	C1—O4—H4A	109.5
C13—C18—H18	119.7	H1A—O1W—H1B	107.4
O2—C19—O1	125.4 (4)

O3—C1—C2—C7	−8.6 (7)	C19—C16—C17—C18	179.6 (4)
O4—C1—C2—C7	173.1 (4)	C16—C17—C18—C13	−1.0 (6)
O3—C1—C2—C3	166.8 (4)	C14—C13—C18—C17	2.5 (6)
O4—C1—C2—C3	−11.4 (6)	C12—C13—C18—C17	−178.2 (3)
C7—C2—C3—C4	1.3 (6)	C17—C16—C19—O2	−167.7 (4)
C1—C2—C3—C4	−174.2 (4)	C15—C16—C19—O2	12.3 (5)
C2—C3—C4—C5	−1.1 (6)	C17—C16—C19—O1	11.0 (5)
C3—C4—C5—C6	0.6 (6)	C15—C16—C19—O1	−168.9 (4)
C3—C4—C5—C8	178.0 (4)	C9—C10—C20—C21	30.9 (6)
C4—C5—C6—C7	−0.2 (6)	C11—C10—C20—C21	−146.3 (4)
C8—C5—C6—C7	−177.6 (4)	C9—C10—C20—C24	−153.5 (4)
C3—C2—C7—C6	−1.0 (6)	C11—C10—C20—C24	29.2 (5)
C1—C2—C7—C6	174.6 (4)	C24—C20—C21—C22	−3.5 (6)
C5—C6—C7—C2	0.5 (6)	C10—C20—C21—C22	172.2 (4)
C6—C5—C8—N1	167.3 (3)	C20—C21—C22—N2	0.6 (6)
C4—C5—C8—N1	−10.0 (5)	N2—C23—C24—C20	0.7 (6)
C6—C5—C8—C9	−11.9 (6)	C21—C20—C24—C23	2.9 (6)
C4—C5—C8—C9	170.7 (4)	C10—C20—C24—C23	−172.8 (4)
N1—C8—C9—C10	−1.8 (6)	C9—C8—N1—C12	1.4 (5)
C5—C8—C9—C10	177.3 (3)	C5—C8—N1—C12	−177.9 (3)
C8—C9—C10—C11	1.2 (5)	C11—C12—N1—C8	−0.4 (5)
C8—C9—C10—C20	−176.1 (3)	C13—C12—N1—C8	−179.9 (3)
C9—C10—C11—C12	−0.3 (5)	C24—C23—N2—C22	−3.6 (6)
C20—C10—C11—C12	177.1 (3)	C24—C23—N2—Cu1	171.8 (3)
C10—C11—C12—N1	−0.1 (6)	C21—C22—N2—C23	3.0 (6)
C10—C11—C12—C13	179.4 (3)	C21—C22—N2—Cu1	−172.4 (3)
N1—C12—C13—C14	28.6 (5)	O1ⁱ—Cu1—N2—C23	−34.5 (3)
C11—C12—C13—C14	−151.0 (4)	O1ⁱⁱ—Cu1—N2—C23	145.5 (3)
N1—C12—C13—C18	−150.7 (4)	O1ⁱ—Cu1—N2—C22	140.8 (3)
C11—C12—C13—C18	29.8 (6)	O1ⁱⁱ—Cu1—N2—C22	−39.2 (3)
C18—C13—C14—C15	−2.7 (6)	O5—C27—N3—C25	179.0 (5)
C12—C13—C14—C15	178.1 (4)	O5—C27—N3—C26	2.5 (8)
C13—C14—C15—C16	1.3 (6)	O6—C30—N4—C29	171.2 (8)
C14—C15—C16—C17	0.3 (6)	O6—C30—N4—C28	−10.0 (14)
C14—C15—C16—C19	−179.8 (4)	O2—C19—O1—Cu1^iv	−6.5 (6)
C15—C16—C17—C18	−0.4 (6)	C16—C19—O1—Cu1^iv	174.9 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O2^v	0.82	1.86	2.584 (4)	146
O1W—H1A···O5^vi	0.85	1.98	2.808 (5)	165
O1W—H1B···O2ⁱ	0.85	1.95	2.758 (4)	159

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (v) x+1/2, −y+5/2, z−1/2; (vi) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO
M_r	1182.73
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.7161 (17), 17.550 (4), 20.947 (4)
β (°)	96.800 (4)
V (Å³)	2816.6 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.27 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.885, 0.913
No. of measured, independent and observed [I > 2σ(I)] reflections	14622, 5226, 3371
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.185, 1.04
No. of reflections	5226
No. of parameters	376
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.93, −0.39

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), XP in SHELXTL and DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O2ⁱ	0.82	1.86	2.584 (4)	146
O1W—H1A···O5ⁱⁱ	0.85	1.98	2.808 (5)	165
O1W—H1B···O2ⁱⁱⁱ	0.85	1.95	2.758 (4)	159

Symmetry codes: (i) x+1/2, −y+5/2, z−1/2; (ii) x+1, y, z; (iii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

The authors are grateful for financial aid from The First Hospital of Jilin University.

References

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