A three-dimensional Cu–Na heteronuclear coordination polymer based on iminodi­acetic acid

A novel Cu–Na heteronuclear three-dimensional coordination polymer, poly[di­aqua­di-μ₅-iminodi­acetato-di-μ₄-iminodi­acet­ato-tricopper(II)disodium(I)], [Cu₃Na₂(C₄H₅NO₄)₄(H₂O)₂]_n, has been prepared by hydro­thermal synthesis. The asymmetric unit contains one and a half copper(II) cations, a sodium cation, two imino­diacetate (ida) ligands and a coordinated water ligand. One of the two independent Cu^II centres is in a general position and is five-coordinated in a distorted square-pyramidal geometry. A [Cu(ida)] unit is formed via a bis-chelating ida ligand and the coordination sphere of the Cu^II atom is completed by two O atoms of two different neigh­bouring [Cu(ida)₂] units. These [Cu(ida)₂] units are associated with the second Cu^II cation, which is located on a crystallographic inversion centre and is coordinated in a distorted square-planar geometry by two chelating ida ligands. The carboxyl­ate groups of the ida ligands act as bridges and connect the [Cu(ida)] and [Cu(ida)₂] building blocks in a 2:1 ratio, forming two-dimensional arrays. These layers are inter­connected into a three-dimensional structure by the sodium ions. Each Na^I cation is coordinated by six O atoms from five ida ligands and a water mol­ecule. When [Cu(ida)], the Na^I cations and [Cu(ida)₂] are viewed as 5-, 5- and 8-connected nodes, respectively, the three-dimensional net­work exhibits a (3².4³.5².6³)₂(3².4³.5².6³)₂(3⁴.6¹⁶.7⁸) topology.

S1. Introduction

In the last two decades, the design and synthesis of coordination polymers with novel structures have attracted considerable inter­est because of their unusual structures and special functional properties with respect to magnetism, optics and gas storage (Chae et al., 2003; Cui et al., 2002; Pan et al., 2003; Sun et al., 2001; Yan et al., 2004; Zhang et al., 2005). In particular, heteronuclear complexes have proven promising for applications as magnetic and optical materials, due to their structural diversity and physical and chemical properties (Li et al., 2007; Qiu et al., 2007). Suitable organic ligands favouring structure-specific self-assembly are the basis for the construction of heteronuclear complexes. The carboxyl­ate group can bridge metal ions to give rise to a wide variety of polynuclear complexes, ranging from discrete entities to three-dimensional systems (Cheng et al., 2007; Dey et al., 2003; Eddaoudi et al., 2002; Fan et al., 2010; Foreman et al., 2000; Ge et al., 2006; Kato & Muto, 1988; Wang et al., 2005). In these complexes, the carboxyl­ate group may adopt many types of bridging conformation, the most important being triatomic syn–syn, anti–anti and syn–anti, and monoatomic bridging. Amino­polycarb­oxy­lic acids contain both amino and carb­oxy­lic acid groups and therefore many potential coordination sites. They may easily chelate to and bridge various metal ions and lead to structurally diverse complexes (Li et al., 2010; Manna et al., 2007; Shen et al., 2007; Stavila et al., 2006).

Iminodi­acetic acid (H₂ida) has been a useful ligand and polymeric derivatives of many transition metals have already been documented (Bresciani-Pahor et al., 1984; Cui et al., 2008; Ding et al., 2009; Li et al., 2010; Manna et al., 2007; Ren et al., 2003; Song et al., 2011; Zhai et al., 2006; Zhou et al., 2011). We report here the crystal structure of poly[di­aqua­tetra-µ₄-iminodi­acetato-copper(II)sodium(I)], (I), a three-dimensional Cu–Na coordination polymer obtained by hydro­thermal synthesis from iminodi­acetic acid, copper(II) chloride and sodium hydroxide.

S2. Experimental

S2.1. Synthesis and crystallization

CuCl₂.2H₂O (0.0171 g, 0.1 mmol), iminodi­acetic acid (0.0266 g, 0.2 mmol), NaOH (0.0168 g, 0.4 mmol), H₂O (0.5 ml) and ethanol (3 ml) were placed in a thick Pyrex tube and heated at 393.15 K for 5 d. After cooling to ambient temperature at a rate of 5 K h^-1, blue block-shaped crystals were collected, washed with anhydrous ethanol and dried at room temperature. The yield is 58% based on CuCl₂.2H₂O. Analysis found: C 24.39, H 3.07, N 7.01%; calculated for C₁₆H₂₄Cu₃N₄Na₂O₁₈: C 24.09, H 3.01, N 7.03%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were included in calculated positions and refined as riding, with C—H = 0.98 Å and with U_iso(H) = 1.2U_eq(C). The H atoms of the aqua ligands and the imino group were located from a difference Fourier map and refined isotropically, with O—H and N—H distances restrained to 0.84 (2) and 0.91 (2) Å, respectively.

S3. Results and discussion

The title heteronuclear compound, (I), displays a three-dimensional coordination network. The asymmetric unit consists of one and a half copper(II) cations, a sodium cation, two iminodi­acetate ligands and a coordinated water molecule. A displacement ellipsoid plot of a section of (I) is shown in Fig. 1, and selected bond lengths and angles are given in Table 2. Compound (I) features two independent Cu^II centres. The Cu1 cation is in a general position and adopts a distorted square-pyramidal geometry, being five-coordinated by three donor atoms (O1, N1 and O3) of the same ida ligand. Two more ida ligands are attached via single O atoms, one by O5 and another by O8ⁱ [symmetry code: (i) x, -y + 3/2, z + 1/2]. The coordination environment around Cu1 corresponds to a slightly distorted square pyramid, with a distortion parameter τ of 0.0812. This parameter is defined as τ = (β - α)/60°, with β and α being the two largest angles subtended at the central atom (Addison et al., 1984); for a perfectly square pyramid, τ = zero. The Cu2 cation is located on a crystallographic inversion centre. Two O- [O7 and O7ⁱⁱ; symmetry code: (ii) -x + 1, -y + 2, -z + 1] and two N-atom donors (N2 and N2ⁱⁱ) from two chelating ida ligands are arranged in a slightly distorted square-planar geometry, with angles of 84.85 (7) [For which atom sequence?] and 95.16 (7)° [For which atom sequence?]. In line with the above discussion, cation Cu1 and the tris-chelating ida ligand can be described as a [Cu(ida)] unit, while cation Cu2 and its two ida ligands can be seen as a [Cu(ida)₂] unit.

The sodium cation is coordinated by six O atoms: O4, O6, O8ⁱ, O4ⁱⁱⁱ and O2^iv are associated with five ida ligands, and O9 with a coordinated water molecule [symmetry codes: (iii) -x, -y + 1, -z + 1; (iv) x - 1, y, z]. Fig. 2 shows the two different coordination modes which the ligands adopt in (I): in the [Cu(ida)] unit, one carboxyl­ate group links Cu^II and Na^I cations in an anti–anti conformation, whereas the second carboxyl­ate group adopts anti–syn and syn–syn conformations with respect to the Cu/Na and Na/Na cations (Fig. 2a). In the [Cu(ida)₂] unit, one carboxyl­ate group bridges Cu and Na centres in a syn–syn conformation, whereas the second carboxyl­ate group is in anti–anti and anti–syn conformations with respect to Cu/Na and Cu/Cu cations (Fig. 2b). Each [Cu(ida)₂] fragment can be seen as a 4-connected node and each [Cu(ida)] fragment as a 2-connected node, with each [Cu(ida)₂] fragment binding to four [Cu(ida)] fragments.

The carboxyl­ate groups act as bridges and link the [Cu(ida)] and [Cu(ida)₂] units in a 2:1 ratio, thus forming a two-dimensional array (Fig. 3) with Cu1···Cu2 separations of 4.0613 (6) and 5.3519 (11) Å. The two-dimensional layers are crosslinked to form a three-dimensional structure by sodium ions.

To understand clearly the different connectivities of [Cu(ida)], [Cu(ida)₂] and the Na^I cations, the rather complicated three-dimensional structure of (I) was simplified with the help of the program TOPOS4.0 (Blatov, 2012). Each [Cu(ida)] unit connects two [Cu(ida)₂] units and three Na^I cations through its carboxyl­ate O atoms, thus representing a 5-connected node. Each [Cu(ida)₂] unit binds to four [Cu(ida)] and four Na^I cations and is 8-connected. Each Na^I cation is linked to three [Cu(ida)] and two [Cu(ida)₂] units and can thus be treated as a 5-connected node. Overall, based on coordinative bonds, (I) can be simplified as a 5,5,8-trinodal network with the point symbol (3².4³.5².6³)₂(3².4³.5².6³)₂(3⁴.6¹⁶.7⁸) (Fig. 4).

Two kinds of inter­layer hydrogen bonds exist, namely O—H···O contacts between the coordinated water molecule and carboxyl­ate groups, and N—H···O hydrogen bonds between amino groups and carboxyl­ate groups. Hydrogen-bonding distances and angles are listed in Table 3.

The optical diffuse refle­cta­nce spectrum of (I) is shown in Fig. 5. Absorption data were calculated from the refle­cta­nce (Wendlandt & Heeht, 1966). Complex (I) exhibits two bands with edges at about 1.09 and 3.34 eV. Two main contributions have to be considered in the spectrum: one is the absorption due to the Cu–Na inter­action, which appears above 3.34 eV, and the second is the coordination field absorption for square-planar Cu^II (d₈), which can be assigned to ca 1.09 eV. The optical band gap of (I) is estimated as 3.34 eV, indicating potential semiconductor properties.

The differential scanning calorimetry–thermogravimetric analysis (DSC–TGA) curve of (I) is illustrated in Fig. 6. The compound is thermally stable up to 425.25 K. The TGA curve displays an initial weight loss of 4.33% between 425.25 and 499.35 K, which corresponds to the loss of the coordinated water molecule (calculated 4.52%). When the temperature is higher than 515.95 K, (I) rapidly decomposes, and the residue at 1073.15 K consists of CuO, Na₂O and elemental carbon.

Related literature

For related literature, see: Addison et al. (1984); Blatov (2012); Bresciani-Pahor, Nardin, Bonomo & Rizzarelli (1984); Chae et al. (2003); Cheng et al. (2007); Cui et al. (2002, 2008); Dey et al. (2003); Ding et al. (2009); Eddaoudi et al. (2002); Fan et al. (2010); Foreman et al. (2000); Ge et al. (2006); Kato & Muto (1988); Li et al. (2007, 2010); Manna et al. (2007); Pan et al. (2003); Qiu et al. (2007); Ren et al. (2003); Shen et al. (2007); Song et al. (2011); Stavila et al. (2006); Sun, D-, Cao, Liang, Shi, Su & Hong (2001); Wang et al. (2005); Wendlandt & Heeht (1966); Yan et al. (2004); Zhai et al. (2006); Zhang et al. (2005); Zhou et al. (2011).

Computing details

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear (Rigaku, 2001); data reduction: CrystalStructure (Rigaku, 2001); 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: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The local coordination of the Cu^II and Na^I cations in (I), with the atom-numbering scheme. H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) x, -y + 3/2, z + 1/2; (ii) -x + 1, -y + 2, -z + 1; (iii) -x, -y + 1, -z + 1; (iv) x - 1, y, z; (v) x + 1, y, z; (vi) x, -y + 3/2, z - 1/2.]

Fig. 2. The two coordination modes of the carboxylate groups in the ida ligands of (I).

Fig. 3. A view of a two-dimensional layer formed by the [Cu(ida)] and [Cu(ida)₂] units of (I).

Fig. 4. The three-dimensional equivalent topological network of (I). The dark (blue in the electronic version of the paper), dark-grey (pink) and light-grey nodes represent Na^I centres and [Cu(ida)] and [Cu(ida)₂] units, respectively.

Fig. 5. The optical diffuse reflectance spectrum for (I).

Fig. 6. The TGA (open squares?) and DSC (solid line?) curves for (I).

Poly[diaquatetra-µ₄-iminodiacetato-copper(II)sodium(I)]

Crystal data

[Cu3Na2(C4H5NO4)4(H2O)2]	F(000) = 802
Mr = 796.99	Dx = 2.138 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 5930 reflections
a = 8.9432 (18) Å	θ = 3.0–27.5°
b = 9.8441 (18) Å	µ = 2.69 mm^−1
c = 14.470 (3) Å	T = 223 K
β = 103.632 (4)°	Block, blue
V = 1238.1 (4) Å^3	0.40 × 0.30 × 0.20 mm
Z = 2

Data collection

Rigaku Saturn diffractometer	2830 independent reflections
Radiation source: fine-focus sealed tube	2473 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 14.63 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −8→11
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −10→12
Tmin = 0.413, Tmax = 0.616	l = −18→15
6895 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0355P)^2 + 0.279P] where P = (Fo^2 + 2Fc^2)/3
2830 reflections	(Δ/σ)max < 0.001
213 parameters	Δρmax = 0.40 e Å^−3
4 restraints	Δρmin = −0.38 e Å^−3

Special details

Experimental. UV-VIS-NIR diffuse reflectance spectra of (I) were measured at room temperature using BaSO₄ as a standard reference on a Shimadzu UV-3150 spectrometer. The absorption (α/S) data were calculated from the reflectance using the Kubelka–Munk function, α/S =(1 - R)²/2R ∞ (Wendlandt & Heeht, 1966). The optical band gaps (Eonset) are obtained by extrapolation of the linear portion of the absorption edges. The thermal stability and decomposition behavior of complex (I) were studied by DSC–TGA. Thermoanalytical measurements was performed using a DCS-TGA microanalyzer of SDT 2960 under a flowing atmosphere of N₂ in the temperature range 293.15–1073.15 K.

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.40735 (3)	0.66243 (3)	0.63796 (2)	0.01676 (10)
Cu2	0.5000	1.0000	0.5000	0.01532 (11)
Na1	0.02804 (11)	0.62325 (10)	0.63873 (7)	0.0218 (2)
O1	0.6107 (2)	0.73572 (18)	0.69804 (13)	0.0237 (4)
O2	0.8569 (2)	0.67501 (18)	0.74221 (13)	0.0247 (4)
O3	0.2469 (2)	0.55865 (17)	0.54944 (12)	0.0217 (4)
O4	0.2022 (2)	0.35365 (17)	0.48315 (13)	0.0241 (4)
O5	0.3487 (2)	0.83648 (17)	0.57967 (13)	0.0232 (4)
O6	0.1070 (2)	0.83560 (18)	0.59614 (14)	0.0256 (4)
O7	0.45416 (19)	0.91655 (17)	0.37452 (11)	0.0190 (4)
O8	0.2646 (2)	0.86522 (18)	0.25060 (12)	0.0217 (4)
O9	−0.0069 (3)	0.3863 (2)	0.63865 (16)	0.0351 (5)
N1	0.5050 (2)	0.4823 (2)	0.67410 (15)	0.0177 (4)
N2	0.2811 (2)	1.0622 (2)	0.46430 (13)	0.0142 (4)
C1	0.7190 (3)	0.6474 (2)	0.71275 (17)	0.0188 (5)
C2	0.6733 (3)	0.5000 (2)	0.69110 (18)	0.0181 (5)
H2A	0.7075	0.4706	0.6347	0.022*
H2B	0.7246	0.4429	0.7447	0.022*
C3	0.4333 (3)	0.3833 (3)	0.60075 (19)	0.0233 (6)
H3A	0.4162	0.2980	0.6316	0.028*
H3B	0.5038	0.3646	0.5597	0.028*
C4	0.2813 (3)	0.4335 (2)	0.54014 (17)	0.0186 (5)
C5	0.2169 (3)	0.8904 (3)	0.57446 (17)	0.0178 (5)
C6	0.2041 (3)	1.0386 (2)	0.54247 (17)	0.0158 (5)
H6A	0.0953	1.0635	0.5214	0.019*
H6B	0.2509	1.0969	0.5964	0.019*
C7	0.2022 (3)	0.9939 (3)	0.37500 (17)	0.0201 (5)
H7A	0.1467	1.0618	0.3303	0.024*
H7B	0.1267	0.9294	0.3885	0.024*
C8	0.3142 (3)	0.9194 (2)	0.32982 (16)	0.0157 (5)
H9	0.036 (4)	0.320 (3)	0.669 (3)	0.066 (13)*
H9A	−0.045 (5)	0.365 (4)	0.5850 (16)	0.064 (14)*
H20	0.277 (3)	1.1511 (17)	0.4548 (19)	0.017 (7)*
H10	0.486 (3)	0.459 (3)	0.7305 (15)	0.026 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01521 (16)	0.01300 (15)	0.02098 (17)	0.00062 (11)	0.00208 (12)	0.00038 (12)
Cu2	0.0122 (2)	0.0177 (2)	0.0151 (2)	0.00113 (15)	0.00143 (16)	−0.00322 (16)
Na1	0.0167 (5)	0.0233 (5)	0.0243 (5)	−0.0007 (4)	0.0023 (4)	0.0043 (4)
O1	0.0192 (10)	0.0184 (9)	0.0315 (10)	−0.0011 (7)	0.0020 (8)	−0.0008 (8)
O2	0.0175 (9)	0.0291 (10)	0.0257 (9)	−0.0025 (8)	0.0017 (7)	−0.0049 (8)
O3	0.0213 (10)	0.0162 (8)	0.0235 (9)	0.0024 (7)	−0.0033 (7)	−0.0017 (7)
O4	0.0264 (10)	0.0179 (9)	0.0239 (9)	−0.0014 (7)	−0.0020 (8)	−0.0034 (7)
O5	0.0175 (9)	0.0163 (8)	0.0358 (10)	0.0028 (7)	0.0064 (8)	0.0050 (8)
O6	0.0191 (10)	0.0228 (9)	0.0361 (10)	0.0000 (7)	0.0089 (8)	0.0109 (8)
O7	0.0141 (9)	0.0234 (9)	0.0184 (8)	0.0024 (7)	0.0013 (7)	−0.0044 (7)
O8	0.0174 (9)	0.0292 (10)	0.0177 (8)	−0.0023 (7)	0.0028 (7)	−0.0066 (8)
O9	0.0461 (14)	0.0271 (11)	0.0310 (12)	0.0037 (10)	0.0066 (11)	0.0041 (10)
N1	0.0140 (11)	0.0192 (10)	0.0192 (10)	0.0001 (8)	0.0025 (8)	0.0004 (9)
N2	0.0160 (10)	0.0120 (9)	0.0143 (9)	0.0011 (8)	0.0031 (8)	0.0005 (8)
C1	0.0188 (13)	0.0236 (13)	0.0137 (11)	−0.0005 (10)	0.0035 (9)	0.0003 (10)
C2	0.0135 (12)	0.0190 (12)	0.0215 (12)	0.0015 (9)	0.0032 (10)	0.0032 (10)
C3	0.0217 (14)	0.0149 (12)	0.0300 (14)	−0.0013 (10)	−0.0005 (11)	−0.0036 (11)
C4	0.0204 (13)	0.0191 (12)	0.0166 (11)	−0.0007 (10)	0.0052 (10)	0.0025 (10)
C5	0.0175 (12)	0.0203 (12)	0.0146 (11)	0.0009 (10)	0.0014 (9)	−0.0010 (10)
C6	0.0138 (12)	0.0153 (11)	0.0190 (11)	0.0009 (9)	0.0052 (9)	−0.0004 (10)
C7	0.0150 (12)	0.0276 (13)	0.0159 (11)	0.0013 (10)	0.0000 (9)	−0.0034 (11)
C8	0.0170 (12)	0.0150 (11)	0.0152 (11)	0.0000 (9)	0.0043 (9)	0.0025 (9)

Geometric parameters (Å, º)

Cu1—O5	1.9270 (17)	O6—C5	1.225 (3)
Cu1—O1	1.9589 (18)	O7—C8	1.267 (3)
Cu1—O3	1.9690 (17)	O8—C8	1.247 (3)
Cu1—N1	1.991 (2)	O8—Cu1^iii	2.3109 (18)
Cu1—O8^i	2.3109 (18)	O8—Na1^iii	2.344 (2)
Cu1—Na1	3.4168 (12)	O9—H9	0.829 (19)
Cu1—Cu2	4.0613 (6)	O9—H9A	0.800 (19)
Cu2—O7^ii	1.9466 (16)	N1—C3	1.472 (3)
Cu2—O7	1.9466 (16)	N1—C2	1.477 (3)
Cu2—N2^ii	2.000 (2)	N1—H10	0.900 (17)
Cu2—N2	2.000 (2)	N2—C6	1.474 (3)
Cu2—Cu1^iii	5.3519 (11)	N2—C7	1.480 (3)
Na1—O6	2.335 (2)	N2—H20	0.885 (17)
Na1—O8^i	2.344 (2)	C1—C2	1.520 (3)
Na1—O9	2.354 (2)	C2—H2A	0.9800
Na1—O4^iv	2.385 (2)	C2—H2B	0.9800
Na1—O2^v	2.434 (2)	C3—C4	1.516 (3)
Na1—O3	2.664 (2)	C3—H3A	0.9800
O1—C1	1.282 (3)	C3—H3B	0.9800
O2—C1	1.236 (3)	C5—C6	1.527 (3)
O2—Na1^vi	2.434 (2)	C6—H6A	0.9800
O3—C4	1.284 (3)	C6—H6B	0.9800
O4—C4	1.235 (3)	C7—C8	1.509 (3)
O4—Na1^iv	2.385 (2)	C7—H7A	0.9800
O5—C5	1.279 (3)	C7—H7B	0.9800
O5—Cu1—O1	89.72 (8)	C4—O3—Na1	120.09 (16)
O5—Cu1—O3	95.46 (7)	Cu1—O3—Na1	93.83 (7)
O1—Cu1—O3	159.67 (8)	C4—O4—Na1^iv	133.80 (16)
O5—Cu1—N1	164.57 (8)	C5—O5—Cu1	123.13 (16)
O1—Cu1—N1	84.70 (8)	C5—O6—Na1	140.55 (17)
O3—Cu1—N1	85.19 (8)	C8—O7—Cu2	115.63 (15)
O5—Cu1—O8^i	105.95 (7)	C8—O8—Cu1^iii	124.26 (16)
O1—Cu1—O8^i	109.85 (7)	C8—O8—Na1^iii	132.95 (16)
O3—Cu1—O8^i	87.64 (7)	Cu1^iii—O8—Na1^iii	94.44 (7)
N1—Cu1—O8^i	89.48 (8)	Na1—O9—H9	137 (3)
O5—Cu1—Na1	86.21 (6)	Na1—O9—H9A	107 (3)
O1—Cu1—Na1	149.15 (6)	H9—O9—H9A	110 (4)
O3—Cu1—Na1	51.07 (6)	C3—N1—C2	116.9 (2)
N1—Cu1—Na1	105.84 (6)	C3—N1—Cu1	108.09 (15)
O8^i—Cu1—Na1	43.16 (5)	C2—N1—Cu1	107.77 (14)
O5—Cu1—Cu2	28.76 (5)	C3—N1—H10	110.2 (19)
O1—Cu1—Cu2	68.98 (5)	C2—N1—H10	106.1 (19)
O3—Cu1—Cu2	107.85 (5)	Cu1—N1—H10	107.4 (19)
N1—Cu1—Cu2	136.89 (6)	C6—N2—C7	112.70 (19)
O8^i—Cu1—Cu2	130.82 (5)	C6—N2—Cu2	111.04 (14)
Na1—Cu1—Cu2	114.312 (18)	C7—N2—Cu2	108.81 (15)
O7^ii—Cu2—O7	180.00 (10)	C6—N2—H20	105.4 (18)
O7^ii—Cu2—N2^ii	84.85 (7)	C7—N2—H20	108.7 (18)
O7—Cu2—N2^ii	95.16 (7)	Cu2—N2—H20	110.1 (18)
O7^ii—Cu2—N2	95.15 (7)	O2—C1—O1	124.2 (2)
O7—Cu2—N2	84.85 (7)	O2—C1—C2	118.6 (2)
N2^ii—Cu2—N2	179.999 (1)	O1—C1—C2	117.2 (2)
O7^ii—Cu2—Cu1	84.80 (5)	N1—C2—C1	111.18 (19)
O7—Cu2—Cu1	95.20 (5)	N1—C2—H2A	109.4
N2^ii—Cu2—Cu1	85.59 (6)	C1—C2—H2A	109.4
N2—Cu2—Cu1	94.41 (6)	N1—C2—H2B	109.4
O7^ii—Cu2—Cu1^iii	171.56 (5)	C1—C2—H2B	109.4
O7—Cu2—Cu1^iii	8.44 (5)	H2A—C2—H2B	108.0
N2^ii—Cu2—Cu1^iii	94.45 (5)	N1—C3—C4	112.3 (2)
N2—Cu2—Cu1^iii	85.55 (5)	N1—C3—H3A	109.1
Cu1—Cu2—Cu1^iii	103.548 (12)	C4—C3—H3A	109.1
O6—Na1—O8^i	81.90 (7)	N1—C3—H3B	109.1
O6—Na1—O9	159.31 (9)	C4—C3—H3B	109.1
O8^i—Na1—O9	98.42 (8)	H3A—C3—H3B	107.9
O6—Na1—O4^iv	88.94 (7)	O4—C4—O3	124.6 (2)
O8^i—Na1—O4^iv	170.84 (8)	O4—C4—C3	118.2 (2)
O9—Na1—O4^iv	90.16 (8)	O3—C4—C3	117.2 (2)
O6—Na1—O2^v	104.36 (8)	O6—C5—O5	125.9 (2)
O8^i—Na1—O2^v	99.28 (7)	O6—C5—C6	119.4 (2)
O9—Na1—O2^v	96.04 (8)	O5—C5—C6	114.6 (2)
O4^iv—Na1—O2^v	82.90 (7)	N2—C6—C5	111.61 (19)
O6—Na1—O3	77.49 (7)	N2—C6—H6A	109.3
O8^i—Na1—O3	72.52 (6)	C5—C6—H6A	109.3
O9—Na1—O3	82.86 (7)	N2—C6—H6B	109.3
O4^iv—Na1—O3	105.60 (7)	C5—C6—H6B	109.3
O2^v—Na1—O3	171.40 (7)	H6A—C6—H6B	108.0
O6—Na1—Cu1	62.35 (5)	N2—C7—C8	111.8 (2)
O8^i—Na1—Cu1	42.40 (5)	N2—C7—H7A	109.3
O9—Na1—Cu1	104.10 (7)	C8—C7—H7A	109.3
O4^iv—Na1—Cu1	132.18 (6)	N2—C7—H7B	109.3
O2^v—Na1—Cu1	138.35 (6)	C8—C7—H7B	109.3
O3—Na1—Cu1	35.10 (4)	H7A—C7—H7B	107.9
C1—O1—Cu1	114.22 (16)	O8—C8—O7	123.7 (2)
C1—O2—Na1^vi	117.55 (16)	O8—C8—C7	118.5 (2)
C4—O3—Cu1	114.20 (15)	O7—C8—C7	117.8 (2)
O5—Cu1—Cu2—O7^ii	81.51 (13)	O4^iv—Na1—O3—C4	−94.50 (17)
O1—Cu1—Cu2—O7^ii	−52.08 (8)	O2^v—Na1—O3—C4	76.8 (5)
O3—Cu1—Cu2—O7^ii	149.24 (7)	Cu1—Na1—O3—C4	120.90 (19)
N1—Cu1—Cu2—O7^ii	−108.34 (10)	O6—Na1—O3—Cu1	59.28 (7)
O8^i—Cu1—Cu2—O7^ii	46.47 (8)	O8^i—Na1—O3—Cu1	−26.05 (7)
Na1—Cu1—Cu2—O7^ii	94.61 (5)	O9—Na1—O3—Cu1	−127.24 (8)
O5—Cu1—Cu2—O7	−98.48 (13)	O4^iv—Na1—O3—Cu1	144.59 (7)
O1—Cu1—Cu2—O7	127.92 (8)	O2^v—Na1—O3—Cu1	−44.1 (5)
O3—Cu1—Cu2—O7	−30.76 (7)	O1—Cu1—O5—C5	−138.0 (2)
N1—Cu1—Cu2—O7	71.66 (10)	O3—Cu1—O5—C5	61.7 (2)
O8^i—Cu1—Cu2—O7	−133.52 (8)	N1—Cu1—O5—C5	153.4 (3)
Na1—Cu1—Cu2—O7	−85.39 (5)	O8^i—Cu1—O5—C5	−27.4 (2)
O5—Cu1—Cu2—N2^ii	166.73 (13)	Na1—Cu1—O5—C5	11.38 (19)
O1—Cu1—Cu2—N2^ii	33.14 (8)	Cu2—Cu1—O5—C5	179.4 (3)
O3—Cu1—Cu2—N2^ii	−125.55 (8)	O8^i—Na1—O6—C5	52.4 (3)
N1—Cu1—Cu2—N2^ii	−23.13 (10)	O9—Na1—O6—C5	−40.0 (4)
O8^i—Cu1—Cu2—N2^ii	131.69 (8)	O4^iv—Na1—O6—C5	−127.6 (3)
Na1—Cu1—Cu2—N2^ii	179.82 (6)	O2^v—Na1—O6—C5	150.0 (3)
O5—Cu1—Cu2—N2	−13.27 (13)	O3—Na1—O6—C5	−21.4 (3)
O1—Cu1—Cu2—N2	−146.86 (8)	Cu1—Na1—O6—C5	12.5 (3)
O3—Cu1—Cu2—N2	54.45 (8)	O7^ii—Cu2—O7—C8	−47.7 (18)
N1—Cu1—Cu2—N2	156.88 (10)	N2^ii—Cu2—O7—C8	172.09 (16)
O8^i—Cu1—Cu2—N2	−48.31 (8)	N2—Cu2—O7—C8	−7.91 (16)
Na1—Cu1—Cu2—N2	−0.18 (6)	Cu1—Cu2—O7—C8	86.07 (16)
O5—Cu1—Cu2—Cu1^iii	−99.75 (12)	Cu1^iii—Cu2—O7—C8	−102.3 (4)
O1—Cu1—Cu2—Cu1^iii	126.66 (6)	O5—Cu1—N1—C3	−77.7 (4)
O3—Cu1—Cu2—Cu1^iii	−32.02 (6)	O1—Cu1—N1—C3	−146.98 (17)
N1—Cu1—Cu2—Cu1^iii	70.40 (9)	O3—Cu1—N1—C3	15.36 (16)
O8^i—Cu1—Cu2—Cu1^iii	−134.79 (6)	O8^i—Cu1—N1—C3	103.03 (17)
Na1—Cu1—Cu2—Cu1^iii	−86.65 (2)	Na1—Cu1—N1—C3	62.57 (17)
O5—Cu1—Na1—O6	−8.52 (8)	Cu2—Cu1—N1—C3	−95.76 (17)
O1—Cu1—Na1—O6	74.56 (12)	O5—Cu1—N1—C2	49.4 (4)
O3—Cu1—Na1—O6	−108.66 (9)	O1—Cu1—N1—C2	−19.82 (15)
N1—Cu1—Na1—O6	−178.71 (9)	O3—Cu1—N1—C2	142.52 (16)
O8^i—Cu1—Na1—O6	109.74 (9)	O8^i—Cu1—N1—C2	−129.81 (15)
Cu2—Cu1—Na1—O6	−14.79 (6)	Na1—Cu1—N1—C2	−170.27 (14)
O5—Cu1—Na1—O8^i	−118.25 (9)	Cu2—Cu1—N1—C2	31.40 (19)
O1—Cu1—Na1—O8^i	−35.18 (13)	O7^ii—Cu2—N2—C6	−45.84 (16)
O3—Cu1—Na1—O8^i	141.60 (10)	O7—Cu2—N2—C6	134.17 (15)
N1—Cu1—Na1—O8^i	71.55 (9)	N2^ii—Cu2—N2—C6	−26 (4)
Cu2—Cu1—Na1—O8^i	−124.53 (7)	Cu1—Cu2—N2—C6	39.32 (15)
O5—Cu1—Na1—O9	154.68 (9)	Cu1^iii—Cu2—N2—C6	142.60 (15)
O1—Cu1—Na1—O9	−122.24 (12)	O7^ii—Cu2—N2—C7	−170.44 (15)
O3—Cu1—Na1—O9	54.53 (9)	O7—Cu2—N2—C7	9.56 (15)
N1—Cu1—Na1—O9	−15.51 (9)	N2^ii—Cu2—N2—C7	−151 (4)
O8^i—Cu1—Na1—O9	−87.07 (9)	Cu1—Cu2—N2—C7	−85.28 (15)
Cu2—Cu1—Na1—O9	148.41 (6)	Cu1^iii—Cu2—N2—C7	18.00 (14)
O5—Cu1—Na1—O4^iv	51.29 (9)	Na1^vi—O2—C1—O1	−117.7 (2)
O1—Cu1—Na1—O4^iv	134.37 (12)	Na1^vi—O2—C1—C2	61.6 (3)
O3—Cu1—Na1—O4^iv	−48.85 (9)	Cu1—O1—C1—O2	173.50 (19)
N1—Cu1—Na1—O4^iv	−118.90 (10)	Cu1—O1—C1—C2	−5.7 (3)
O8^i—Cu1—Na1—O4^iv	169.55 (11)	C3—N1—C2—C1	143.4 (2)
Cu2—Cu1—Na1—O4^iv	45.02 (8)	Cu1—N1—C2—C1	21.5 (2)
O5—Cu1—Na1—O2^v	−88.86 (10)	O2—C1—C2—N1	169.5 (2)
O1—Cu1—Na1—O2^v	−5.78 (15)	O1—C1—C2—N1	−11.2 (3)
O3—Cu1—Na1—O2^v	170.99 (11)	C2—N1—C3—C4	−139.3 (2)
N1—Cu1—Na1—O2^v	100.95 (11)	Cu1—N1—C3—C4	−17.6 (3)
O8^i—Cu1—Na1—O2^v	29.40 (10)	Na1^iv—O4—C4—O3	4.2 (4)
Cu2—Cu1—Na1—O2^v	−95.13 (9)	Na1^iv—O4—C4—C3	−172.99 (17)
O5—Cu1—Na1—O3	100.15 (9)	Cu1—O3—C4—O4	−174.40 (19)
O1—Cu1—Na1—O3	−176.77 (12)	Na1—O3—C4—O4	75.4 (3)
N1—Cu1—Na1—O3	−70.05 (9)	Cu1—O3—C4—C3	2.8 (3)
O8^i—Cu1—Na1—O3	−141.60 (10)	Na1—O3—C4—C3	−107.3 (2)
Cu2—Cu1—Na1—O3	93.87 (7)	N1—C3—C4—O4	−172.2 (2)
O5—Cu1—O1—C1	−150.64 (18)	N1—C3—C4—O3	10.4 (3)
O3—Cu1—O1—C1	−45.5 (3)	Na1—O6—C5—O5	−9.0 (4)
N1—Cu1—O1—C1	14.95 (17)	Na1—O6—C5—C6	174.21 (18)
O8^i—Cu1—O1—C1	102.48 (17)	Cu1—O5—C5—O6	−7.7 (4)
Na1—Cu1—O1—C1	127.25 (16)	Cu1—O5—C5—C6	169.23 (15)
Cu2—Cu1—O1—C1	−130.24 (18)	C7—N2—C6—C5	67.7 (2)
O5—Cu1—O3—C4	153.84 (17)	Cu2—N2—C6—C5	−54.7 (2)
O1—Cu1—O3—C4	49.7 (3)	O6—C5—C6—N2	−141.4 (2)
N1—Cu1—O3—C4	−10.68 (18)	O5—C5—C6—N2	41.5 (3)
O8^i—Cu1—O3—C4	−100.35 (17)	C6—N2—C7—C8	−133.5 (2)
Na1—Cu1—O3—C4	−125.52 (19)	Cu2—N2—C7—C8	−9.9 (2)
Cu2—Cu1—O3—C4	127.27 (16)	Cu1^iii—O8—C8—O7	−29.6 (3)
O5—Cu1—O3—Na1	−80.64 (7)	Na1^iii—O8—C8—O7	−169.25 (16)
O1—Cu1—O3—Na1	175.24 (18)	Cu1^iii—O8—C8—C7	149.74 (17)
N1—Cu1—O3—Na1	114.84 (8)	Na1^iii—O8—C8—C7	10.1 (3)
O8^i—Cu1—O3—Na1	25.17 (6)	Cu2—O7—C8—O8	−176.69 (18)
Cu2—Cu1—O3—Na1	−107.21 (5)	Cu2—O7—C8—C7	3.9 (3)
O6—Na1—O3—C4	−179.82 (18)	N2—C7—C8—O8	−175.0 (2)
O8^i—Na1—O3—C4	94.85 (17)	N2—C7—C8—O7	4.4 (3)
O9—Na1—O3—C4	−6.34 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O2^vii	0.83 (2)	2.01 (2)	2.830 (3)	173 (4)
O9—H9A···O3^iv	0.80 (2)	2.44 (3)	3.091 (3)	139 (4)
N2—H20···O4^viii	0.89 (2)	2.17 (2)	2.982 (3)	152 (2)
N1—H10···O7^i	0.90 (2)	2.49 (2)	3.199 (3)	136 (2)

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