A one-dimensional heterometallic coordination polymer with a three-dimensional supra­molecular framework: poly[μ₂-aqua-diaqua­(2,2′-bipyrid­yl)(μ₅-2-sulfonato­butane­dioato)copper(II)sodium(I)]

The title compound, [CuNa(C₄H₃O₇S)(C₁₀H₈N₂)(H₂O)₃]_n, consists of one Cu^II cation, one Na^I cation, one 2-sulfonato­butane­dioate trianion (SSC³⁻), one 2,2′-bipyridyl (bpy) ligand and three coordinated water mol­ecules as the building unit. The coordination of the Cu^II cation is composed of two pyridyl N atoms, one water O atom and two carboxyl­ate O atoms in a distorted square-pyramidal coordination geometry with an axial elongation. The Na^I cation is six-coordinated by three water mol­ecules and three carboxyl­ate O atoms from three SSC³⁻ ligands in a distorted octa­hedral geometry. Two SSC³⁻ ligands link two Cu^II cations to form a Cu₂(SSC)₂(bpy)₂ macrocyclic unit lying across an inversion centre, which is further linked by Na^I cations via Na—O bonds to give a one-dimensional chain. Inter­chain hydrogen bonds link these chains to form a two-dimensional layer, which is further extended into a three-dimensional supra­molecular framework through π–π stacking inter­actions. The thermal stability of the title compound has also been investigated.

S1. Comment

Coordination polymers constructed from metal cations or metal clusters with multifunctional organic ligands have attracted much attention in recent decades, not only for their aesthetically pleasing structures but also for their potential applications in areas such as gas storage and separation, catalysis, photoluminescence, molecular magnetism and nonlinear optics (Eddaoudi et al., 2001; Yoon et al., 2012; Allendorf et al., 2009; Wang et al., 2008; Zhang et al., 2009). Compared with the generally used carboxylate ligands, organosulfonate ligands have so far been less investigated. The sulfonate group has three potential O-atom coordination sites and is usually regarded as a weak ligating group with flexible coordination modes, which may form various coordination polymers or supramolecules with interesting structures through extensive hydrogen bonds (Xiao et al., 2009; Mahmoudkhani & Shimizu, 2007; Cai, 2004). Nevertheless, we are interested in bifunctional sulfonate–carboxylate ligands because they can exhibit discriminative coordination abilities. While some rigid sulfonate–carboxylate ligands, such as 5-sulfoisophthalic acid (Sun et al., 2003; Liu et al., 2010), 2-sulfoterephthalic acid (Horike et al. 2006), 4,8-disulfonylnaphthalene-2,6-dicarboxylic acid (Liu et al., 2012) and 4-sulfobenzoic acid (Zhang & Zhu, 2006) and their metal complexes have been reported, only one flexible sulfonate–carboxylate ligand of 2-sulfobutanedioic acid (H₃SSC) and two of its sodium–zinc heterometallic compounds have been reported, in which the H₃SSC ligand displays various coordination modes resulting in different frameworks (Liu et al., 2011). Further research on the flexible H₃SSC ligand in other metal complexes is needed for comprehensive understanding of H₃SSC coordination chemistry. We report herein the synthesis and crystal structure of the title heterometallic compound, (I), incorporating the H₃SSC ligand.

The asymmetric unit of (I) consists of one Na^I cation, one Cu^II cation, one SSC^3- ligand, one 2,2'-bipyridyl (bpy) molecule and three aqua ligands. As depicted in Fig. 1, the Cu1 cation is five-coordinated by two carboxylate O atoms [O1 and O3ⁱ; symmetry code: (i) -x + 2, -y + 1, -z] from two SSC^3- ligands and two N atoms from one bpy ligand in a distorted square-planar geometry, with a water molecule (O8) in the apical position. The apical Cu—O distance is considerably longer than the equatorial ones (Table 1); such axial elongation could be attributed to the strong Jahn–Teller distortion of the copper(II) cation. As shown in Fig. 1, three O atoms from three SSC^3- ligands and three water molecules complete the distorted octahedral coordination environment for the Na1 cation. Two water molecules (O8 and O10) and two carboxylate O atoms [O1 and O4ⁱⁱ; symmetry code: (ii) x - 1, y, z] form the equatorial plane and the axial positions are occupied by one carboxylate O and one coordinating water molecule. The NaO₆ octahedron is distorted, with O—Na—O angles varying from 74.09 (7) to 169.96 (9)° (Table 1). It is noted that one of the coordinating water molecules (O8) acts as a µ₂-briding ligand between the Cu1 and Na1 cations, while the other two water molecules are terminal coordinating ligands. The SSC^3- ligand employs its two µ₂-carboxylate O atoms (O1 and O4) and one monondentate carboxylate O atom (O3) to bridge three Na^I and two Cu^II cations. Carboxylate atom O2 and the sulfonate O atoms are not involved in coordination but are engaged in hydrogen bonding.

As shown in Fig. 2, two symmetry-related SSC^3- ligands link two Cu1 cations (Cu1 and Cu1ⁱ) to form a centrosymmetric Cu₂(SSC)₂(bpy)₂ macrocyclic unit with a 14-membered ring. These Cu₂(SSC)₂(bpy)₂ units are linked by Na1 cations through Na1—O1, Na1—O8, Na1—O4ⁱ and Na1—O4ⁱⁱ bonds to form a one-dimensional chain (Fig. 2), which is further reinforced by hydrogen bonds [O8···O10ⁱⁱⁱ, O8···O2ⁱⁱ, O9···O5ⁱⁱ, O9···O7 and O10···O3; symmetry code: (iii) -x + 1, -y + 1, -z] (Table 2). These one-dimensional chains are linked by an O10···O5^iv [symmetry code: (iv) -x + 2, -y + 2, -z] hydrogen bond to form a two-dimensional layer along the ab plane (Fig. 3). These two-dimensional layers are stacked along the c direction to produce the crystal packing (Fig. 4). In the three-dimensional crystal packing, there are interlayer π–π stacking interactions between the pyridine rings, which are arranged in an offset fashion with a dihedral angle of 2.07 (12)°, a face-to-face distance of 3.4863 (10) Å and a centroid-to-centroid distance of 3.7775 (15) Å. The extensive hydrogen bonds and π–π stacking interactions are responsible for the final three-dimensional supramolecular architecture.

To the best of our knowledge, only two compounds, namely [Na₂Zn₃(µ3-OH)₂(SSC)₂(H₂O)₄]_n [Reference?] and [Na₄Zn(SSC)₂(H₂O)_3.5]_n [Reference?], based on the H₃SSC ligand have been reported to date. In both compounds, the two-dimensional anionic layers constructed from the zinc cations and SSC^3- ligands are linked by sodium cations in various manners to generate quite different three-dimensional architectures (Liu et al., 2011), which are very different from the structure of (I). In addition, for the nonsulfonated analogue (succinate) of the H₃SSC ligand, three copper(II) compounds with succinate (SC) and bpy ligands have been reported. In the discrete dinuclear structure of [Cu₂(SC)(bpy)₄]SC.12H₂O (Lin & Xu, 2009) and the one-dimensional chain of {[Cu₂(SC)(µ₂-H₂O)₂(bpy)₂]NO₃}_n (Zhang et al., 2004), the SC^2- ligand, in a bidentate bridging mode, bridges two metal cations, while the {[Cu₂(SC)(bpy)₂(H₂O)](ClO₄)₂.0.5H₂O}_n compound possesses a cationic two-dimensional layer charge-balanced with perchlorate anions (Ghoshal et al., 2004), in which the SC^2- ligand binds to five metal cations. All are different from the corresponding sulfonated-analogue based compound, which indicates that the sulfonate group has a significant influence on the structure of the final product, although the sulfonate group is uncoordinated in (I).

The results of thermal analyses are represented by the curves in Fig. S1 in the Supplementary materials. Compound (I) exhibits two main steps of weight loss. The first step (333–413 K) corresponds to release of the three coordinated water molecules (weight loss, measured = 12.02% and theoretical = 10.99%). A sharp continual weight loss then occurrs at 518 K, which is attributed to decomposition of the organic ligands.

Related literature

For related literature, see: Allendorf et al. (2009); Cai (2004); Eddaoudi et al. (2001); Ghoshal et al. (2004); Horike et al. (2006); Lin & Xu (2009); Liu et al. (2010, 2011, 2012); Mahmoudkhani & Shimizu (2007); Sun et al. (2003); Wang et al. (2008); Xiao et al. (2009); Zhang & Zhu (2006); Zhang et al. (2004, 2009).

S2. Experimental

An ethanol solution (5 ml) of 2,2'-bipyridyl (32.4 mg, 0.2 mmol) was carefully layered on top of a mixture of an aqueous solution (5 ml) of Cu(CH₃CO₂)₂.H₂O (49.9 mg, 0.25 mmol), a 2-sulfobutanedioic acid solution (141.6 mg, 0.5 mmol) and sodium hydroxide (20 mg, 0.5 mmol). Blue block-shaped crystals were obtained after a week. The crystalline product was filtered, washed with ethanol and dried at ambient temperature [yield: 43%, based on Cu(CH₃CO₂)₂.H₂O].

S3. Refinement

H atoms bonded to C atoms were placed in calculated positions and treated using a riding-model approximation, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene H atoms, and C—H = 0.98 Å and U_iso(H) = 1.2U_eq(C) for methylidyne H atoms. Water H atoms were located in a difference map and refined with a restraint of O—H = 0.82 (2) Å and U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted for clarity, except for the water H atoms, which are shown as small spheres of arbitrary radii. Dashed lines indicate intramolecular hydrogen bonds. [Symmetry codes: (i) -x + 2, -y + 1, -z; (ii) x - 1, y, z.]
	Fig. 2. A perspective view of the macrocyclic [Cu(SSC)2(bpy)2]^- unit of (I) and the one-dimensional chain. [Symmetry codes: (i) -x + 2, -y + 1, -z; (iii) -x + 1, -y + 1, -z.]
	Fig. 3. A perspective view of the two-dimensional layered structure of (I). Dashed lines indicate hydrogen bonds. [Symmetry code: (iv) -x + 2, -y + 2, -z.]
	Fig. 4. A view of the packing for (I), viewed along the b axis. Dotted lines between aromatic rings indicate π–π stacking interactions.

poly[µ₂-aqua-diaqua(2,2'-bipyridyl)(µ₅- 2-sulfonatobutanedioato)copper(II)sodium(I)]

Crystal data

[NaCu(C4H3O7S)(C10H8N2)(H2O)3]	Z = 2
Mr = 491.89	F(000) = 502
Triclinic, P1	Dx = 1.803 Mg m^−3
a = 7.1560 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8692 (6) Å	Cell parameters from 4042 reflections
c = 12.9585 (8) Å	θ = 2.5–28.2°
α = 95.853 (1)°	µ = 1.41 mm^−1
β = 90.544 (1)°	T = 296 K
γ = 95.643 (1)°	Block, blue
V = 905.82 (10) Å^3	0.36 × 0.28 × 0.21 mm

Data collection

Bruker APEXII area-detector diffractometer	4360 independent reflections
Radiation source: fine-focus sealed tube	3688 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ω scans	θmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.632, Tmax = 0.757	k = −13→13
8529 measured reflections	l = −16→17

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0451P)^2 + 0.6176P] where P = (Fo^2 + 2Fc^2)/3
4360 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.56 e Å^−3
6 restraints	Δρmin = −0.30 e Å^−3

Special details

Experimental. Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 3428, 2926, 1608, 1495, 1473, 1445, 1400, 1323, 1283, 1213, 1151, 1080, 949, 859, 766, 730, 594, 546, 523.

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
Na1	0.63906 (13)	0.64665 (10)	0.05549 (7)	0.0304 (2)
Cu1	0.81668 (4)	0.49559 (2)	0.246359 (19)	0.02049 (8)
S1	1.17897 (8)	0.95225 (6)	0.20643 (5)	0.02834 (14)
O1	0.9098 (2)	0.65127 (15)	0.16923 (12)	0.0242 (3)
O2	1.1698 (2)	0.60962 (17)	0.24859 (13)	0.0295 (4)
O3	1.1190 (2)	0.63830 (16)	−0.13295 (12)	0.0265 (3)
O4	1.3196 (2)	0.59098 (17)	−0.01191 (13)	0.0331 (4)
O5	1.3305 (3)	1.04046 (17)	0.16576 (16)	0.0395 (4)
O6	1.2095 (4)	0.9343 (2)	0.31395 (15)	0.0579 (6)
O7	0.9968 (3)	0.9934 (2)	0.1843 (2)	0.0581 (6)
O8	0.5138 (2)	0.52714 (19)	0.20275 (14)	0.0323 (4)
H8A	0.460 (4)	0.455 (2)	0.178 (2)	0.048*
H8B	0.433 (4)	0.570 (3)	0.226 (2)	0.048*
O9	0.6444 (3)	0.8784 (3)	0.1173 (3)	0.0762 (9)
H9A	0.569 (6)	0.937 (4)	0.120 (4)	0.114*
H9B	0.755 (4)	0.909 (5)	0.130 (4)	0.114*
O10	0.7298 (3)	0.6957 (2)	−0.11602 (16)	0.0372 (4)
H10A	0.728 (5)	0.778 (2)	−0.119 (3)	0.056*
H10B	0.837 (3)	0.683 (4)	−0.131 (3)	0.056*
N1	0.7477 (3)	0.34523 (18)	0.33602 (14)	0.0239 (4)
N2	0.8048 (3)	0.60898 (18)	0.38449 (14)	0.0229 (4)
C1	1.0864 (3)	0.6747 (2)	0.18858 (16)	0.0220 (4)
C2	1.1978 (3)	0.7868 (2)	0.13611 (16)	0.0230 (4)
H2	1.3302	0.7697	0.1403	0.028*
C3	1.1499 (3)	0.7881 (2)	0.02207 (17)	0.0257 (4)
H3A	1.2155	0.8688	−0.0029	0.031*
H3B	1.0161	0.7942	0.0141	0.031*
C4	1.2026 (3)	0.6609 (2)	−0.04387 (16)	0.0215 (4)
C5	0.7137 (4)	0.2119 (2)	0.30334 (19)	0.0343 (6)
H5	0.7210	0.1840	0.2329	0.041*
C6	0.6680 (4)	0.1145 (3)	0.3707 (2)	0.0375 (6)
H6	0.6426	0.0227	0.3459	0.045*
C7	0.6608 (4)	0.1556 (2)	0.4745 (2)	0.0340 (5)
H7	0.6325	0.0915	0.5213	0.041*
C8	0.6959 (3)	0.2932 (2)	0.50965 (18)	0.0300 (5)
H8	0.6925	0.3224	0.5801	0.036*
C9	0.7361 (3)	0.3862 (2)	0.43834 (16)	0.0223 (4)
C10	0.7706 (3)	0.5357 (2)	0.46573 (16)	0.0221 (4)
C11	0.7681 (4)	0.5981 (2)	0.56641 (18)	0.0322 (5)
H11	0.7450	0.5460	0.6217	0.039*
C12	0.8005 (4)	0.7388 (3)	0.5832 (2)	0.0359 (6)
H12	0.7988	0.7828	0.6501	0.043*
C13	0.8352 (4)	0.8131 (3)	0.5005 (2)	0.0347 (5)
H13	0.8579	0.9080	0.5107	0.042*
C14	0.8359 (3)	0.7459 (2)	0.40237 (19)	0.0306 (5)
H14	0.8587	0.7969	0.3465	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0299 (5)	0.0307 (5)	0.0310 (5)	0.0046 (4)	−0.0034 (4)	0.0035 (4)
Cu1	0.02715 (15)	0.01869 (14)	0.01526 (13)	0.00161 (10)	0.00060 (9)	0.00058 (9)
S1	0.0349 (3)	0.0203 (3)	0.0273 (3)	−0.0012 (2)	0.0037 (2)	−0.0063 (2)
O1	0.0249 (8)	0.0236 (8)	0.0237 (8)	−0.0001 (6)	−0.0012 (6)	0.0033 (6)
O2	0.0292 (8)	0.0333 (9)	0.0269 (8)	0.0060 (7)	−0.0006 (7)	0.0052 (7)
O3	0.0347 (9)	0.0259 (8)	0.0186 (8)	0.0072 (6)	−0.0008 (6)	−0.0020 (6)
O4	0.0369 (9)	0.0328 (9)	0.0291 (9)	0.0123 (7)	−0.0065 (7)	−0.0063 (7)
O5	0.0413 (10)	0.0233 (8)	0.0521 (12)	−0.0041 (7)	0.0041 (8)	0.0014 (8)
O6	0.1062 (19)	0.0370 (11)	0.0264 (10)	−0.0022 (11)	−0.0031 (11)	−0.0074 (8)
O7	0.0384 (11)	0.0394 (11)	0.0920 (18)	0.0112 (9)	−0.0033 (11)	−0.0222 (11)
O8	0.0243 (9)	0.0373 (10)	0.0349 (10)	0.0073 (7)	−0.0004 (7)	−0.0023 (8)
O9	0.0345 (12)	0.0430 (13)	0.144 (3)	0.0030 (10)	−0.0047 (15)	−0.0234 (15)
O10	0.0336 (9)	0.0334 (9)	0.0452 (11)	0.0032 (8)	0.0021 (8)	0.0073 (8)
N1	0.0319 (10)	0.0200 (9)	0.0193 (9)	0.0012 (7)	−0.0001 (7)	0.0006 (7)
N2	0.0257 (9)	0.0210 (9)	0.0213 (9)	0.0028 (7)	0.0026 (7)	−0.0016 (7)
C1	0.0290 (11)	0.0180 (10)	0.0173 (10)	−0.0002 (8)	0.0051 (8)	−0.0051 (7)
C2	0.0279 (11)	0.0200 (10)	0.0201 (10)	0.0004 (8)	0.0013 (8)	−0.0011 (8)
C3	0.0372 (12)	0.0212 (10)	0.0190 (10)	0.0068 (9)	0.0012 (9)	0.0001 (8)
C4	0.0259 (11)	0.0212 (10)	0.0166 (10)	−0.0009 (8)	0.0031 (8)	0.0011 (8)
C5	0.0541 (16)	0.0234 (11)	0.0234 (12)	−0.0015 (10)	−0.0010 (10)	−0.0024 (9)
C6	0.0539 (16)	0.0211 (11)	0.0361 (14)	−0.0027 (11)	−0.0027 (12)	0.0026 (10)
C7	0.0410 (14)	0.0279 (12)	0.0332 (13)	−0.0027 (10)	0.0002 (10)	0.0106 (10)
C8	0.0369 (13)	0.0313 (12)	0.0216 (11)	0.0009 (10)	0.0003 (9)	0.0037 (9)
C9	0.0226 (10)	0.0238 (10)	0.0199 (10)	0.0012 (8)	−0.0003 (8)	0.0006 (8)
C10	0.0221 (10)	0.0231 (10)	0.0211 (10)	0.0036 (8)	0.0003 (8)	0.0010 (8)
C11	0.0441 (14)	0.0312 (12)	0.0208 (11)	0.0055 (10)	0.0017 (10)	−0.0011 (9)
C12	0.0457 (15)	0.0348 (13)	0.0252 (12)	0.0074 (11)	−0.0003 (10)	−0.0093 (10)
C13	0.0406 (14)	0.0224 (11)	0.0389 (14)	0.0034 (10)	0.0030 (11)	−0.0078 (10)
C14	0.0365 (13)	0.0239 (11)	0.0312 (13)	0.0022 (9)	0.0069 (10)	0.0017 (9)

Geometric parameters (Å, º)

Na1—O9	2.342 (3)	N1—C5	1.338 (3)
Na1—O4^i	2.4034 (19)	N1—C9	1.352 (3)
Na1—O10	2.404 (2)	N2—C14	1.344 (3)
Na1—O1	2.4174 (18)	N2—C10	1.348 (3)
Na1—O4^ii	2.4306 (19)	C1—C2	1.521 (3)
Na1—O8	2.474 (2)	C2—C3	1.516 (3)
Cu1—O3^i	1.9631 (15)	C2—H2	0.9800
Cu1—O1	1.9820 (15)	C3—C4	1.526 (3)
Cu1—N1	2.0035 (18)	C3—H3A	0.9700
Cu1—N2	2.0190 (18)	C3—H3B	0.9700
Cu1—O8	2.2932 (17)	C5—C6	1.381 (3)
S1—O7	1.438 (2)	C5—H5	0.9300
S1—O6	1.440 (2)	C6—C7	1.369 (4)
S1—O5	1.4594 (18)	C6—H6	0.9300
S1—C2	1.805 (2)	C7—C8	1.385 (3)
O1—C1	1.280 (3)	C7—H7	0.9300
O2—C1	1.241 (3)	C8—C9	1.380 (3)
O3—C4	1.284 (3)	C8—H8	0.9300
O3—Cu1^i	1.9631 (15)	C9—C10	1.477 (3)
O4—C4	1.231 (3)	C10—C11	1.386 (3)
O4—Na1^i	2.4034 (19)	C11—C12	1.379 (4)
O4—Na1^iii	2.4306 (19)	C11—H11	0.9300
O8—H8A	0.810 (18)	C12—C13	1.371 (4)
O8—H8B	0.791 (18)	C12—H12	0.9300
O9—H9A	0.827 (19)	C13—C14	1.373 (3)
O9—H9B	0.827 (19)	C13—H13	0.9300
O10—H10A	0.816 (18)	C14—H14	0.9300
O10—H10B	0.813 (18)
O9—Na1—O4^i	169.96 (9)	C9—N1—Cu1	115.09 (14)
O9—Na1—O10	93.28 (11)	C14—N2—C10	118.68 (19)
O4^i—Na1—O10	90.46 (7)	C14—N2—Cu1	126.62 (16)
O9—Na1—O1	84.31 (9)	C10—N2—Cu1	114.61 (14)
O4^i—Na1—O1	85.65 (6)	O2—C1—O1	122.52 (19)
O10—Na1—O1	111.41 (7)	O2—C1—C2	118.90 (19)
O9—Na1—O4^ii	102.81 (8)	O1—C1—C2	118.59 (19)
O4^i—Na1—O4^ii	86.62 (7)	C3—C2—C1	114.58 (18)
O10—Na1—O4^ii	87.93 (7)	C3—C2—S1	110.92 (15)
O1—Na1—O4^ii	159.19 (7)	C1—C2—S1	110.67 (14)
O9—Na1—O8	103.37 (11)	C3—C2—H2	106.7
O4^i—Na1—O8	74.09 (7)	C1—C2—H2	106.7
O10—Na1—O8	162.37 (8)	S1—C2—H2	106.7
O1—Na1—O8	76.49 (6)	C2—C3—C4	112.57 (18)
O4^ii—Na1—O8	82.81 (7)	C2—C3—H3A	109.1
O3^i—Cu1—O1	91.89 (7)	C4—C3—H3A	109.1
O3^i—Cu1—N1	90.71 (7)	C2—C3—H3B	109.1
O1—Cu1—N1	173.28 (7)	C4—C3—H3B	109.1
O3^i—Cu1—N2	164.01 (7)	H3A—C3—H3B	107.8
O1—Cu1—N2	95.24 (7)	O4—C4—O3	125.1 (2)
N1—Cu1—N2	80.75 (7)	O4—C4—C3	120.59 (19)
O3^i—Cu1—O8	101.93 (7)	O3—C4—C3	114.34 (19)
O1—Cu1—O8	89.89 (7)	N1—C5—C6	122.2 (2)
N1—Cu1—O8	95.63 (7)	N1—C5—H5	118.9
N2—Cu1—O8	92.40 (7)	C6—C5—H5	118.9
O3^i—Cu1—Na1	83.56 (5)	C7—C6—C5	118.8 (2)
O7—S1—O6	113.75 (16)	C7—C6—H6	120.6
O7—S1—O5	112.31 (13)	C5—C6—H6	120.6
O6—S1—O5	112.33 (14)	C6—C7—C8	119.7 (2)
O7—S1—C2	108.26 (11)	C6—C7—H7	120.2
O6—S1—C2	105.56 (11)	C8—C7—H7	120.2
O5—S1—C2	103.82 (11)	C9—C8—C7	118.9 (2)
C1—O1—Cu1	106.85 (13)	C9—C8—H8	120.6
C1—O1—Na1	151.58 (14)	C7—C8—H8	120.6
Cu1—O1—Na1	97.49 (6)	N1—C9—C8	121.4 (2)
C4—O3—Cu1^i	125.31 (14)	N1—C9—C10	114.62 (18)
C4—O4—Na1^i	130.17 (14)	C8—C9—C10	124.0 (2)
C4—O4—Na1^iii	132.73 (15)	N2—C10—C11	121.6 (2)
Na1^i—O4—Na1^iii	93.38 (7)	N2—C10—C9	114.78 (18)
Cu1—O8—Na1	88.20 (6)	C11—C10—C9	123.6 (2)
Cu1—O8—H8A	109 (2)	C12—C11—C10	118.9 (2)
Na1—O8—H8A	106 (2)	C12—C11—H11	120.6
Cu1—O8—H8B	138 (2)	C10—C11—H11	120.6
Na1—O8—H8B	106 (2)	C13—C12—C11	119.4 (2)
H8A—O8—H8B	104 (3)	C13—C12—H12	120.3
Na1—O9—H9A	136 (4)	C11—C12—H12	120.3
Na1—O9—H9B	109 (4)	C12—C13—C14	119.2 (2)
H9A—O9—H9B	114 (5)	C12—C13—H13	120.4
Na1—O10—H10A	108 (3)	C14—C13—H13	120.4
Na1—O10—H10B	116 (3)	N2—C14—C13	122.2 (2)
H10A—O10—H10B	103 (3)	N2—C14—H14	118.9
C5—N1—C9	118.98 (19)	C13—C14—H14	118.9
C5—N1—Cu1	125.93 (16)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O10^iv	0.81 (2)	2.01 (2)	2.801 (3)	166 (3)
O8—H8B···O2^ii	0.79 (2)	1.98 (2)	2.720 (2)	156 (3)
O9—H9A···O5^ii	0.83 (2)	2.13 (3)	2.920 (3)	159 (5)
O9—H9B···O7	0.83 (2)	1.94 (2)	2.756 (3)	170 (5)
O10—H10A···O5^v	0.82 (2)	2.03 (2)	2.818 (3)	162 (4)
O10—H10B···O3	0.81 (2)	2.11 (2)	2.903 (3)	166 (4)

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